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Review

Heterotridentate Organomonophosphines in Pt(κ3–X1P1X2)(Y) (X1,2 = N1,2 or S1,2), Pt(κ3–P1N1X1)(Y) (X1 = O, C, S or Se) Pt(κ3–P1S1Cl1)(Cl) and Pt(κ3–P1Si1N1)(OL)—Structural Aspects

by
Milan Melník
1,2,* and
Peter Mikuš
1,3
1
Comenius University Bratislava, Faculty of Pharmacy, Department of Pharmaceutical Analysis and Nuclear Pharmacy, Odbojárov 10, SK-832 32 Bratislava, Slovakia
2
Slovak Technical University, Faculty of Chemical and Food Technology, Radlinskeho 9, SK-812 37 Bratislava, Slovakia
3
Comenius University Bratislava, Faculty of Pharmacy, Toxicological and Antidoping Centre, Odbojárov 10, SK-832 32 Bratislava, Slovakia
*
Author to whom correspondence should be addressed.
Crystals 2022, 12(12), 1772; https://doi.org/10.3390/cryst12121772
Submission received: 21 November 2022 / Revised: 29 November 2022 / Accepted: 1 December 2022 / Published: 6 December 2022
(This article belongs to the Special Issue Feature Papers in Crystal Engineering in 2022)
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Abstract

This review covers twenty four Pt(II) complexes of the inner coordination sphere Pt(κ3–P1 N1N2)(Y), (Y = Cl, CL); Pt(κ3–P1N1X1)(Y), (X1 = O1 and Y = P2L, Cl, I); (X1 = C1 and Y = NL, Cl); (X1 = S1 and Y = Cl, I); (X1 = Se1 and Y = Cl); Pt(κ3–N1P1N2)(Cl), Pt(κ3–S1P1S2)(Cl), Pt(κ3–P1S1Cl1)(Cl) and Pt(κ3–P1Si1N1)(OL). These complexes are crystallized in three crystal classes: monoclinic (16 examples), triclinic (5 examples), and orthorhombic (3 examples). Each κ3–ligand creates two metallocyclic rings with various combinations of the respective metallocyclic rings. If the common central ligating atom is N1, the 5 + 5 membered, 5 + 5, 5 + 6, 6 + 5, and 6 + 6; if the common central ligating atom is P1: 5 + 5, and 6 + 6; if the common central ligating atom is S1 or Si1, 5 + 6-membered. The structural parameters (Pt-L, L-Pt-L) are analysed and discussed with an attention to the distortion of a square-planar geometry about the Pt(II) atoms as well as trans-influence. The sums of the Pt-L (x = 4) bond distances the growing with the covalent radius of the Y atoms. Noticeably, the distortion of the square-planar geometry is growing with the decreasing size of the inner coordination sphere about the Pt(II) atom. There is a relation between the degree of distortion (Ʈ4) and the numbers of the metallocycles rings. The distortion diminishing is in the order of: 0.058 (5 + 5) > 0.037 (6 + 5) > 0.023 (5 + 6) > 0.022 (6 + 6) membered.

1. Introduction

Platinum exists in a wide range of oxidation states from zero to +6, including non-integral, Pt(2.25), Pt(2.81), Pt(3.25) and Pt(3.5). Of these, particularly in four- and six- coordinated, +2 and +4 oxidation states are the most common. The many platinum coordination complexes have been surveyed [1,2,3], converting the crystallographic and structural data of almost two thousand monomeric examples.
About 10% of these complexes exist as isomers. Their structural data were analysed and classified [4]. Included are distortion (65%) cis-trans (30%), mixed isomers (cis-trans and distortion) and ligand isomers. Despite the importance of cis-trans geometry in the chemistry of Pt(II), the distortion isomers atom is far more common.
Recently, we detail analysed the structural data of distortion isomers of the cis-Pt(II) complexes, and none of the cis-isomer has a trans-partner. The distortion isomers differ mostly in Pt-L distances as well as the values of the L-Pt-L angles [5]. Another review has focused on the ligand isomers of Pt(II) complex [6].
Organomonophosphines as a soft P-donor ligand are very useful for building a wide variety of platinum complexes. Research activity in this field is always very active. Organophosphines on the basis of donor atoms can be divided into four sub-groups: homodentate (P, PP, PPP, PPPP), heterobi- (PO, PN, PB, PS) and heterotridentate (POP, PNP, PCP, PBP, PSP, PSiP) as well as tetradentate (P4, P3Si, P2N2, P2S2, P2C2, PN3) [7,8,9].
The aim of this survey is to correlate the structural parameters available for heterotridentate organomonophosphines of the types: Pt(κ3–P1N1X1)(Y) (X = N2, O1, C1, S1, Se1), Pt(κ3–N1P1N2)(Cl), Pt(κ3–S1P1S2)(Cl), Pt(κ3–P1S1Cl1)(Y) and Pt(κ3–P1Si1N1)(OL).

2. Results and Discussion

2.1. Pt(κ3–P1N1N2)(Y) Derivatives

There are nine examples of the Pt(κ3–P1N1N2)(Y) type, and their structural parameters are gathered in Table 1 (A: Pt(κ3-P1N1N2)(Y)). In triclinic [Pt{κ3–But2P1(CH2)(C5H3N1)(CH2)N2Et2}(Cl)].C6H6 (at 120 K) [10], heterotridentate κ3–P1N1N2 ligand creates two five-membered metallocyclic rings with the central common ligating N1 atom of P1C2N1C2N2 type with the values of the respective rings of 85.5° (P1-Pt-N1) and 83.4° (N1-Pt-N2). The Cl− completed a square-planar geometry about Pt(II) atom. The remaining L-Pt-L bond angles open in the sequence 92.6° (N2–Pt–Cl) < 98.5° (P1–Pt–Cl) < 168.0° (P1–Pt–N2) < 176.0° (N1–Pt–Cl). The Pt-L bond distance elongates in the order: 1.997 Å (Pt–N1 trans to Cl) < 2.149 Å (Pt–N2 trans to P1) < 2.236 Å (Pt–P1) < 2.296 Å (Pt–Cl).
In following six complexes: triclinic [Pt{κ3–Ph2P1(C7H5N1)(C2H2O)N2(C6H4OH)}(CH3)].CHCl3 (at 150 K) [11], monoclinic [Pt{κ3–Ph2P1(C7H5N1)(C2H2O)N2(C6H6OH)}(CH3)].1.5toluene (at 150 K) [11] [Pt{κ3–Ph2P1(C7H5N1)(C3H6)N2(C7H5O2)}(CH3)].2 toluene (at 150 K) [11], monoclinic [Pt{κ3–Ph2P1(C7H5N1)(C6H4)N2(C10H9NO3)}(CH3)].Et2O (at 150 K) [12], monoclinic [Pt{κ3–Ph2P1(C7H5N1)(C5H7O)N2(C10H10N2)}(CH3)].H2O (at 93 K) [13], and monoclinic [Pt{κ3–Ph2P1(C7H5N1)(C2H2O)N2(C6H4OH)}(CH3)].CHCl3 (at 150 K) [14] each κ3–P1N1N2 ligand creates six- and five-metallocyclic rings with the centre common ligating N1 atom of the P1C3N1C2N2 type. In each complex the methyl group completed a distorted square-planar geometry about each Pt(II) atom. The mean values for the respective chelate rings are: 93.8(±4.0)° (P1-Pt-N1) and 80.3(±1.2)° (N1-Pt-N2). The remaining L-Pt-L bind angles open in the sequence (mean values): 90.9(1.9)° (P1–Pt–C) < 94.4(2.2)° (N2–Pt–C) < 173.4(1.3)° (N1–Pt–C) < 173.7(4.7)° (P1–Pt–N2). The Pt-L bond distance elongates in the order (mean values): 2.060(±23)Å (Pt–C, trans to N1) < 2.066(±21)Å (Pt–N1, trans to C) < 2.079(±15)Å (Pt–N2, trans to P1) < 2.186(±7)Å (Pt–P1, trans to N2).
The structure of the triclinic [Pt{κ3–Ph2P1(C7H5N1)(NC5H4N2)}(Cl)] (at 150 K) is shown in Figure 1, as an example [15]. As can be seen, the κ3–P1N1N2 ligand forms six- and five-membered metallocyclic rings of the P1C3N1NCN2 type with the centre common ligating N1 atom. The chlorido ligand completed a distorted square-planar geometry about the Pt(II)atom. The values of the respective rings are 95.8° (P1-Pt-N1) and 79.3° (N1-Pt-N2). The remaining bind angles open in the sequence: 90.8° (P1–Pt–Cl) < 94.2° (N2–Pt–Cl) < 173.0° (P1–Pt–N2) < 173.4° (N1–Pt–Cl). The Pt-L bond distance elongates in the order: 2.053 Å (Pt–N1, trans to Cl) < 2.086 Å (Pt–N2, trans to P1) < 2.200Å (Pt–P1) < 2.297 Å (Pt–Cl).
In the monoclinic [Pt{κ3–Ph2P1(C7H6N1)(C7H8N)(C7H8N2)}(Cl)].PF6 [16] the κ3–P1N1N2 ligand creates two six-membered metallocyclic rings with the centre common ligating N1 atom of the P1C3N1C3N2 type. The values of the chelate rings are 93.3° (P1-Pt-N1) and 85.6°(N1-Pt-N2). The remaining bind angles open in the order: 90.9° (N2–Pt–Cl) < 91.8° (P1–Pt–Cl) < 174.0° (N1–Pt–Cl) < 178.7° (P1–Pt–N2). The Pt-L bond distance elongates in the order: 2.104 Å (Pt–N2, trans to P1) < 2.120 Å (Pt–N1, trans to Cl) < 2.234 Å (Pt–P1) < 2.284 Å (Pt–Cl).

2.2. Pt(κ3–P1N1O1)(Y) Derivatives

Structural data for five Pt(κ3–P1N1O1)(Y) derivatives are gathered in Table 1 (B: Pt(κ3–P1N1O1)(Y)). In the triclinic [Pt{κ3–Ph2P1(C8H6N1)(NC7H5O1)}{κ1–Ph2P(C15H13N2O)}].CH2Cl2 (at 200 K) [17] the κ3–P1N1O1 ligand with monodentate PL donor ligand builds up a distorted square-planar geometry about the Pt(II) atom (PtP1N1O1P). The κ3–P1N1O1 ligand forms two five-membered metallocyclic rings with the centre common ligating N1 atom of the P1C2N1NCO1 type, with the values of the chelate rings of 83.6° (P1-Pt-N1) and 78.8° (N1-Pt-O1). The remaining L-Pt-L bind angles open in the sequence: 94.7° (O1–Pt–P) < 102.9° (P1–Pt–P) < 162.4° (P1–Pt–O1) < 173.3° (N1–Pt–P). The Pt-L bond distance elongates in the order: 1.985 Å (Pt–N1, trans to P) < 2.050 Å (Pt–O1, trans to P1) < 2.233 Å (Pt–P1) < 2.261 Å (Pt–P).
In the monoclinic [Pt{κ3–Ph2P1(C6H4N1)(C7H4ClO1)}{P(p-tolyl)3}].ClO4 (at 200 K) [18] a distorted square-planar geometry about the Pt(II) atom is built up by the κ3–P1N1O1 ligand with P(p-tolyl)3. The κ3–P1N1O1 ligand forms five- and six-membered metallocyclic rings with the common N1 atom of the P1C2N1C3O1 type with the values of the chelate rings of 82.7° (P1-Pt-N1) and 91.2° (N1-Pt-O1). The remaining L-Pt-L bind angles open in the order: 86.5° (O1–Pt–P) < 99.6° (P1–Pt–P) < 172.1° (P1–Pt–O1) < 177.7° (N1–Pt–P). The Pt-L bond distance elongates in the order: 2.03 Å (Pt–O1 trans to P1) < 2.05 Å (Pt–N1 trans to P) < 2.21(1) Å (Pt–P1) < 2.269 Å (Pt–P).
Two monoclinics [Pt{κ3–Ph2P1(C6H4N1)(C8H7OO1)}(Z)] (Z = Cl or I) are isostructural [18]. The κ3–P1N1O1 with Z builds up distorted square-planar geometry about the Pt(II) atoms. The values of P1C2N1C3O1 metallocyclic rings are 83.6° (P1-Pt-N1) and 92.3° (N1-Pt-O1) when Z = Cl; for Z = I, the values are 84.8° and 91.9°, respectively. The remaining L-Pt-L bind angles open in the order: 87.9° (O1–Pt–Cl) < 93.5° (P1–Pt–Cl) < 178.5° (P1–Pt–O1) < 178.9° (N1–Pt–Cl); vs. 89.2° (O1–Pt–I) < 92.6° (P1–Pt–I) < 176.6° (P1–Pt–O1) < 178.2° (N1–Pt–I). As can be seen, the L-Pt-L angles for Cl− complex are somewhat larger than for I− complex, except O1-Pt-X. The Pt-L bond distance elongates in the order: 2.005 Å (Pt–N1, trans to Cl) < 2.080 Å (Pt–O1, trans to P1) < 2.195 Å (Pt–P1) < 2.303 Å (Pt–Cl); vs. 2.011 Å (Pt–N1, trans to I) < 2.045 Å (Pt–O1, trans to P1) < 2.207 Å (Pt–P1) < 2.620 Å (Pt–I).
In orthorhombic [Pt{κ3–Ph2P1(C8H7N1O1)}(Cl)] [19], the κ3–P1N1O1 ligand form two six-membered metallocyclic rings of the P1C3N1C3O1 type with the central common ligating N1 atom. The clorido ligands completed a distorted square-planar geometry about the Pt(II) atom. The values of the chelate rings are 94.8° (P1-Pt-N1) and 93.3° (N1-Pt-O1). The remaining L-Pt-L bind angles open in the order: 84.0° (O1–Pt–Cl) < 89.1° (P1–Pt–Cl) < 174.8° (N1–Pt–Cl) < 175.5° (P1–Pt–O1). The Pt-L bond distance elongates in the order: 1.88 Å (Pt–N1, trans to Cl) < 2.14 Å (Pt–O1, trans to P1) < 2.206 Å (Pt–P1) < 2.386 Å (Pt–Cl).

2.3. Pt(κ3–P1N1C1)(Y) Derivatives

There are two monoclinic complexes [Pt{κ3–Ph2P1(C7H6N1 = NCC1C5H6)}(Cl)] (Figure 2) (at 120 K) [20] and [Pt{κ3–Ph2P1(C7H5N1)(C7H8C1)}(py)].BF4 (at 100 K) [21] (Table 1 (C: Pt(κ3–P1N1C1)(Y))). In the former complex, the κ3–P1N1C1 ligand forms two five-membered metallocyclic rings of the P1C2N1NCC1 type, with the values of the chelate rings of 85.2° (P1-Pt-N1) and 78.7° (N1-Pt-C1), respectively. The clorido ligands completed a distorted square-planar geometry about the Pt(II) atom. The remaining L-Pt-L bind angles open in the order: 84.0° (C1–Pt–Cl) < 99.9° (P1–Pt–Cl) < 163.9° (P1–Pt–C1) < 174.6° (N1–Pt–Cl). The Pt-L bond distance elongates in the order: 1.972 Å (Pt–N1, trans to Cl) < 2.023 Å (Pt–C1, trans to P1) < 2.291 Å (Pt–P1) < 2.309 Å (Pt–Cl).
In the complex cation, the N-donor atom of pyridine completed the inner coordination sphere about the Pt(II) atom (PtP1N1C1N). The κ3–ligand creates six- and five-membered metallocycles of the P1C3N1C2C1 type. The values of the respective chelate rings are 92.1° (P1-Pt-N1) and 82.3° (N1-Pt-C1). The remaining L-Pt-L bind angles open in the order: 92.4° (P1–Pt–N) < 93.6° (C1–Pt–N) < 170.7° (N1-Pt-Cl) < 174.3° (P1–Pt–C1). The Pt-L bond distance elongates in the order: 2.000 Å (Pt-N1 trans to N) < 2.026 Å (Pt–N1) < 2.035 Å (Pt–C1, trans to P1) < 2.292 Å (Pt–P1).

2.4. Pt(κ3–P1N1S1)(Y) Derivatives

There are two such derivatives, monoclinic [Pt{κ3–Ph2P1 (C6H4CHN1NC(S1) NHMe} (Cl)] [22] and triclinic [Pt{κ3–Ph2P1(C7H5N1)(MeS1)(ButNH2)}(I)] [23] (Table 1 (D: Pt(κ3–P1N1S1)(Y))). In the monoclinic complex, the κ3–P1N1S1 ligand with chlorido builds up distorted square-planar geometry about the Pt(II) atom. The κ3–P1N1S1 ligand in the chlorido complex creates six- and five-membered metallocyclic rings with the centre common ligating N1 atom of the P1C3N1NCS1 type. The values of the chelate rings are 95.8° (P1-Pt-N1) and 84.9° (N1-Pt-S1). The remaining L-Pt-L bind angles open in the order: 89.5° (P1–Pt–Cl) < 89.8° (S1–Pt–Cl) < 174.4° (N1–Pt–Cl) < 177.8° (P1-Pt-S1). The Pt-L bond distance elongates in the order: 2.03 Å (Pt–N1, trans to Cl) < 2.239 Å (Pt–P1, trans to S1) < 2.298 Å (Pt–S1) < 2.304 Å (Pt–Cl).
In the triclinic complex, the κ3–P1N1S1 ligand creates two six-membered metallocyclic rings of the P1C3N1C3S1 type with the values of the chelate rings of 89.1° (P1-Pt-N1) and 93.2° (N1-Pt-S1). The remaining L-Pt-L bind angles open in the order: 84.2° (S1–Pt–I) < 93.6° (P1–Pt–I) < 175.4° (N1–Pt–I) < 176.2° (P1–Pt–S1). The Pt-L bond distance elongates in the order: 2.056 Å (Pt–N1, trans to I) < 2.240 Å (Pt–P1, trans to S1) < 2.363 Å (Pt–S1) < 2.580 Å (Pt–I).

2.5. Pt(κ3–P1N1Se1)(Y) Derivatives

Monoclinic [Pt{κ3–Ph2P1(C7H5N1)(C3H6Se1)(Ph)}(Cl)].BF4 (at 150 K) [24] is the only example of κ3–P1N1Se1 type. The Cl− anion completed a distorted square-planar geometry about the Pt(II) atom. The κ3–P1N1Se1 ligand creates two six-membered metallocyclic rings with the centre common ligating N1 atom of the P1C3N1C3Se1 type. The values of the chelate rings are 87.5° (P1-Pt-N1) and 95.7° (N1-Pt-Se1). The remaining L-Pt-L bind angles open in the order: 83.7° (Se1–Pt–Cl) < 93.0° (P1–Pt–Cl) < 176.7° (P1–Pt–Se1) < 178.8° (N1–Pt–Cl). The Pt-L bond distance elongates in the order: 2.028 Å (Pt–N1, trans to Cl) < 2.308 Å (Pt–Cl) < 2.407 Å (Pt–P1, trans to Se1) < 2.489 Å (Pt–Se1).

2.6. Pt(κ3–N1P1N2)(Cl) and Pt(κ3–S1P1S2)(Cl) Derivatives

Their structural data are gathered in Table 2. In orthorhombic [Pt{κ3–N1(C6H6)N(C6H10)NP1(Pri)(C6H6)N2}(Cl)]Cl.H2O (at 150 K) [25] heterotridentate κ3–N1P1N2 ligand with Cl− anion builds up a distorted square-planar geometry about the Pt(II) atom. The κ3–N1P1N2 ligand forms two six-membered metallocyclic rings with the centre common ligating P1 atom of the N1C2NP1NC2N2 type. The values of the chelate rings are: 91.1° (N1-Pt-P1) and 91.0° (P1-Pt-N2). The remaining L-Pt-L bind angles open in the order: 90.4° (N1–Pt–Cl) < 91.0° (N2–Pt–Cl) < 173.0° (P1–Pt–Cl) < 175.4° (N1–Pt–N2). The Pt-L bond distance elongates in the order: 2.035 Å (Pt–N1, trans to N2) < 2.039 Å (Pt–N2) < 2.187 Å (Pt–P1. trans to Cl) < 2.375 Å (Pt–Cl).
Two monoclinic complexes [Pt{κ3–PriS1(C6H4)P1(C6H4SPri)(C6H4)S2}(Cl)] (Figure 3) (at 123 K) [26] and [Pt{κ3–ButS1(C6H4)P1(C6H4SBut)(C6H4)S2}(Cl)].0.5CHCl3 (at 123 K) [26] have a similar structure. In each, the κ3–S1P1S2 ligand forms two five-membered metallocycles with the centre common ligating P1 atom of the S1C2P1C2S2 type. In the former complex, the values of the chelate rings are 88.2° (S1-Pt-P1) and 87.7° (P1-Pt-S2). The remaining L-Pt-L angles open in the order: 90.8° (S2–Pt–Cl) < 93.0° (S1–Pt–Cl) < 162.1° (S1–Pt–S2) < 178.3° (P1–Pt–Cl). In the latter complex, the L-Pt-L angles open in the order: 88.7° (S1–Pt–P1) < 88.8° (P1–Pt–S2) < 90.8° (S2–Pt–Cl) < 158.7° (S1–Pt–S2) < 178.6° (P1–Pt–Cl).
The Pt-L bond distance elongates in the order (mean values): 2.194(±4) Å (Pt–P1, trans to Cl) < 2.288 Å (Pt-S1 trans to S2) < 2.294 (±3) Å (Pt–S2) < 2.367 (±7) Å (Pt–Cl).

2.7. Pt(κ3–P1S1Cl1)(Cl) and Pt(κ3–P1Si1N1)(OL) Derivatives

Their structural data are given in Table 2. In the orthorhombic [Pt{κ3–Ph2P1(C23H28S1)(B)(Ph2)Cl1}(Cl)]·2CH2Cl2 (Figure 4) (at 123 K) [27] heterotridentate κ3–P1S1Cl1 ligand with the Cl− anion builds up a distorted square-planar geometry about the Pt(II) atom. The κ3–P1S1Cl1 forms five- and six-metallocyclic rings of the P1C2S1C2BCl1 type. The values of the respective chelate rings are 87.9° (P1-Pt-S1) and 87.1° (S1-Pt-Cl1). The remaining L-Pt-L bind angles open in the order: 91.7° (Cl1–Pt–Cl) < 93.4° (P1–Pt–Cl) < 173.3° (S1–Pt–Cl) < 174.7° (P1–Pt–Cl1). The Pt-L bond distance elongates in the order: 2.212 Å (Pt–P1, trans to Cl1) < 2.243 Å (Pt–S1, trans to Cl) < 2.321 Å (Pt–Cl) < 2.391 Å (Pt–Cl1).
Structure of the monoclinic [Pt{κ3–cyh2P1(C6H4)Si1(CH3)(C7H6)N1(CH3)2}(OSO2CF3)] [28] is shown in Figure 5. The κ3–P1Si1N1 ligand with OL builds up a distorted square-planar geometry about the Pt(II) atom. The chelate ligand forms five- and six-membered metallocyclic rings with the central common ligating Si1 atom of the P1C2Si1C3N1 type. The values of the respective angles are 85.8° (P1-Pt-Si1) and 82.7° (Si1-Pt-N1). The remaining L-Pt-L bind angles open in the order: 86.4° (N1–Pt–O) < 95.0° (P1–Pt–O) < 169.2° (P1–Pt–N1) < 179.0° (Si1–Pt–O). The Pt-L bond distance elongates in the order: 2.177 Å (Pt–N1, trans to P1) < 2.228 Å (Pt–P1) < 2.260 Å (Pt–Si1, trans to O) < 2.353 Å (Pt–O).
As can be seen (Table 1 and Table 2), organomonophosphines as heterotridentate ligands used (except for the P atom) a wide variety of heteroatoms for coordination to Pt(II) atoms. There are twenty four Pt(II) complexes which crystalized in three crystal classes: monoclinic (16 examples), triclinic (5 examples) and orthorhombic (3 examples). Each heterotridentate ligand forms two metallocyclic rings. The metallocycles based on the heteroatom involved in these metallocycles can divided into four subgroups:
  • 5 + 5—membered: P1C2P1C2N2 (1 example), P1C2N1NCO1 (1 example), P1C2N1NCC1 (1 example) and S1C2N1C2S2 (2 examples)
  • 6 + 5—membered: P1C3N1C2N2 (6 examples), P1C3N1NCN2, (1 example), P1C3N1C2C1, (1 example) and P1C3N1NCS1 (1 example)
  • 5 + 6—membered: P1C2N1C3O1 (3 examples), P1C2S1C2BCl1, (1 example) and P1C2Si1C3N1 (1 example)
  • 6 + 6—membered: P1C3N1C3N2, P1C3N1C3O1, P1C3N1C3S1, P1C3N1C3Se1 and N1C2NP1NC2N2 (each 1 example)
In the Pt(κ3–P1N1X)(Y), (X = N2, O1, C1, S1, or Se1) complexes (Table 1) the total mean values of Pt-L bind distance elongate in the sequences:
Pt-P1 (trans to X): 2.20 Å (N2) < 2.22 Å (O1) < 2.23 Å (C1) < 2.24 Å (S1) < 2.40 Å (Se1);
Pt-X1 (trans to P1): 2.03 Å (C1) < 2.065 Å (O1) < 2.085 Å (N2) < 2.330 Å (S1) < 2.489 Å (Se1);
Pt-N1 (trans to Y): 1.985 Å (P2) < 2.00 Å (N3) < 2.02 Å (Cl) < 2.03 Å (I) < 2.065 Å (C2);
Pt-Y1 (trans to N1): 2.005 Å (N3) < 2.068 Å (C2) < 2.260 Å (P2) < 2.304 Å (Cl) < 2.600 Å (I).
These correspond quite were with the trans influence of the X1 /ligand.

3. Conclusions

This review covers 24 monomeric four-coordinated Pt(II) complexes. The inner coordination sphere about the Pt(II) atoms are built up heterotridentate organomonophosphines with the monodentate atom/ligand. The κ3–-ligands create a variety of metallocyclic rings.
There are at least two contributing factors to the size of the L-Pt-L chelate bond angles, both ligand based. One is steric constraints imposed by the ligand, and the other is the need to accommodate the imposed ring size. The effect of both steric and electronic can be seen from the values of the chelate angles (mean values):
5 + 5—membered
P1C2N1/N1NCO1 83.6/78.8°; P1C2N1/N1NCC1 85.2/78.7°; S1C2P1/P1C2S2 88.5/88.2°; P1C2N1/N1C2N2 85.5/83.4°
6 + 5—membered
P1C3N1/N1C2C1 92.1/82.3°; P1C3N1/N1C2N2 93.8/80.2°; P1C3N1/N1NCN2 94.5/82.5°; P1C3N1/N1NCS1 95.8/84.9°;
5 + 6 membered
P1C2Si1/Si1C3N1 85.6/82.7°; P1C2S1/S1C2BCl1 87.9/87.1°; P1C2N1/N1C3O1 83.7/91.8°
6 + 6 membered
N1C2NP1/P1NC2N2 91.1/91.0°; P1C3N1/N1C3O1 94.8/93.3°; P1C3N1/N1C3S1 89.1/93.2°; P1C3N1/N1C3Se1 82.5/95.2°
It is well known that in four coordinates, Pt(II) prefer a square-planar geometry. The utility of a simple metric to assess molecular shape and degree of distortion as well is best exemplified by the Ʈ4 parameter for a square-planar geometry by the equation introduced by the [29].
Ʈ4 = 360 − (α + β)/360 for square-planar, and
Ʈ4 = 360 − (α + β)/141 for tetrahedral
The values for Ʈ4 range from 0.00 for perfect square-planar geometry to 1.00 for a perfect tetrahedral, since 360 − 2 (109.5)/141.
Summary of the total mean values of trans- α- L-Pt-L (L are terminal ligating atoms of the respective chelate) and trans- β- L’-Pt-Y (L’ central ligating atom of the rings) bond angles and of Ʈ4 are given in Table 3.
As can be seen (Table 3) where β-angles are almost constant, the α-angles are mostly growing with the membered of the respective rings. The distortion of the square- planar geometry about the Pt(II) atoms is diminishing.
In general, distortion of the square-planar geometry about the Pt(II) atoms is diminishing in the order of the respective complexes (total mean values): 0.059 (PtS1P1S2)(Y) > 0.051 (PtP1N1C1)(Y) > 0.033 (PtP1Si1N1)(Y) ~ 0.033 (PtP1S1Cl1)(Y) > 0.032 (PtN1P1N2)(Y) > 0.028 (PtP1N1O1)(Y) > 0.023 (PtP1N1S1)(Y) > 0.012 (PtP1N1Se1)(Y)
Noticeably, in some complexes there is a relationship between the inner coordination sphere about the Pt(II) atom and the degree of distortion. When the volume of the inner coordination sphere is growing, the distortion is lowering and vice versa, as can be seen from the parameters of the sums of the four Pt-L bond distances and parameters of Ʈ4. The (Pt-L(x4) vs. Ʈ4) are:
Pt(κ3–P1N1N2)(Y): 8.394 Å vs. 0.036(Y = CL); 8.647 Å vs. 0.034 (Y = Cl)
Pt(κ3–P1N1O2)(Y): 8.556 Å vs. 0.048(Y = PL); 8.594 Å vs. 0.011 (Y = Cl); 8.883 Å vs. 0.014 (Y = I)
Pt(κ3–P1N1S1)(Y): 8.891 Å vs. 0.023 (Y = Cl); 9.231 Å vs. 0.022 (Y = I)
Pt(κ3–P1N1Se1)(Cl): 9.226 Å vs. 0.012

Author Contributions

The authors contributed equally. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the Ministry of Education and Science of Slovakia grant number VEGA 1/0514/22, KEGA 027UK-4/2020, and APVV-15-0585.

Acknowledgments

This work was supported by the Comenius University Bratislava, Faculty of Pharmacy, and by projects of the Ministry of Education and Science, Slovakia, VEGA 1/0514/22, KEGA 027UK-4/2020, and APVV-15-0585.

Conflicts of Interest

The authors declare no conflict of interest.

Abbreviations

But2P1(CH2)(C5H3N1)(CH2)N2Et2(2-(di-t-butylphosphinomethyl)-6-diethyl-aminomethyl)pyridine)
ButS1(C6H4)P1(C6H4SBut)(C6H4)S2)(2-((2-(t-butylsulfanyl)phenyl)(2-t-butyl-sulfanyl)phenyl)phosphino)benzenethiazato
cyh2P1(C6H4)Si1(CH3)(C7H6N1(Me2))((2-(dicyclohexylphosphanyl)(2-(dimethyl-amino)methyl)phenyl)methylsilyl)
mmonoclinic
N1(C6H6)N(C6H10)NP1(Pri)(C6H6)N2(2-isopropyl-1,3-bis(2-pyridylmethyl)-octahydro-1H-1,3,2-benzodiazophosphore
ororthorhombic
Ph2P1((C6H4CHN1NC(S1).NHMe)(2-(diphenylphosphino)thiosemicarbazide
Ph2P1(C23H28S1)(B(Ph2)Cl1)((2,7-di-t-butyl-5-((chloro)(diphenyl)-25-boranyl)-9,9-dimethyl-9H-thioxantin-4-yl)(diphonylphosphine)
Ph2P1(C6H4N1)(C7H4ClO1)(C7H8N2)(4-chloro-2-(((2-(diphenylphosphino)phenylimino)methylphenylate
Ph2P1(C6H4N1)(C8H7NOO1)(2-(((2-(diphenylphosphino)phenylimino)methyl-4-methoxyphenylato)
Ph2P1(C7H5N1)(C2H2O)N2(C6H4OH)(N-(2-(diphenylphosphinobenzylidene)-N-(2-hydroxyphenyl)glycinamidato)
Ph2P1(C7H5N1)(C2H2O)N2(C6H4OH)(N2-(2-(diphenylphosphino)benzylidene)-N-(3-hydroxyphenyl)glycinamidato
Ph2P1(C7H5N1)(C2H2O)N2(C7H6OH)(N-(2-(diphenylphosphino)benzylidene)-N-(2-hydroxymethylphenyl)glycine-amidato)
Ph2P1(C7H5N1)(C3H6)N2(C7H5O2)(N-(2-((2-(diphenylphosphino)benzylidene)amino)propyl)-2-hydroxybenzamidato)
Ph2P1(C7H5N1)(C5H7O)N2(C10H10N2)R7C-(N-(5,7-(dimethyl-1,8-naphtylridin-2-yl)-N2-(2-(diphenylphosphinyl)benzylidene) valinamidato)
Ph2P1(C7H5N1)(C6H4)N2(C10H9NO3)(N2-benzyloxycarbinol)-N-(2-(((2-(diphenylphosphanyl)phenyl)methylidene) amino)phenyl)glycinamide)
Ph2P1(C7H5N1)(C7H8C1)(C7H8N2)(2-(1b)-1-(((2-diphenylphosphinobenzylidene)amine) ethyl)phenyl)
Ph2P1(C7H5N1)(MeS1)(ButNH2)(N-{N-[2-(diphenylphosphino)benzylidene)]-D/L-methionyl}-terc-butylamine
Ph2P1(C7H5N1)(NC5H4N2)(2-(2-(diphenylphosphino)benzylidene)-1-(pyridine-2-yl)diazanido
Ph2P1(C7H5N1C3H6Se1(Ph)(N-(2-(diphenylphosphino)benzylidene)-N-(3-(phenylseleno)propyl)amine
Ph2P1(C7H5N1O1)(2-diphenylphosphino)-2-aminobenzaldehyde)
Ph2P1(C7H6N1)(C7H8N)(C7H8N2)(N2-(2-(diphenylphosphino)benzyl)-N,N-bis(2-pyridyl-2-ethyl)amine)
Ph2P1(C7H6N1)(NC7H5O1)Ph2P2(C15H13N2O)(N-(2-(diphenylphosphino)-1-phenylformyl)benzohydiazino)-N-(2-(diphenylphosphino)-1-phenylvinyl)benzohydeazone)
Ph2P1(C7H6N1 = NCC1C5H6)(2-((2-(diphenylphosphino)-4-methylphenyl)diazinyl)-5-methylphenyl)pyridine
PriS1(C6H4)P1(C6H4SPri).(C6H4)S2)(2-(((2-(isopropysulfanyl)phenyl)(2-isopropylsulfanyl)phenyl)phosphino)benzenethiazato)
pypyridine
trtriclinic

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Crystals 12 01772 g001
Figure 1. Structure of [Pt{κ3–Ph2P1(C7H6N1)(NC5H5N2)}(Cl)] [15].
Figure 1. Structure of [Pt{κ3–Ph2P1(C7H6N1)(NC5H5N2)}(Cl)] [15].
Crystals 12 01772 g001
Crystals 12 01772 g002
Figure 2. Structure of [Pt{κ3–Ph2P1(C7H6N1 = NCC1C5H6)}(Cl)] [20].
Figure 2. Structure of [Pt{κ3–Ph2P1(C7H6N1 = NCC1C5H6)}(Cl)] [20].
Crystals 12 01772 g002
Crystals 12 01772 g003
Figure 3. Structure of [Pt{κ3–PriS1(C6H4)P1(C6H4SPri)(C6H4)S2}(Cl)] [26].
Figure 3. Structure of [Pt{κ3–PriS1(C6H4)P1(C6H4SPri)(C6H4)S2}(Cl)] [26].
Crystals 12 01772 g003
Crystals 12 01772 g004
Figure 4. Structure of Pt{κ3–Ph2P1(C23H28S1)(B)(Ph2)Cl1}(Cl)] [27].
Figure 4. Structure of Pt{κ3–Ph2P1(C23H28S1)(B)(Ph2)Cl1}(Cl)] [27].
Crystals 12 01772 g004
Crystals 12 01772 g005
Figure 5. Structure of [Pt{κ3–cyh2P1(C6H4)Si1(CH3)(C7H6)N1(CH3)2}(OSO2CF3)] [28].
Figure 5. Structure of [Pt{κ3–cyh2P1(C6H4)Si1(CH3)(C7H6)N1(CH3)2}(OSO2CF3)] [28].
Crystals 12 01772 g005
Table 1. Structural data for Pt(κ3–P1N1N2)(Y) and Pt(κ3–P1N1X1)(Y) (X1 = O1, C1, S1 or Se1), (Y = variable monodentate atoms/ligands) a.
Table 1. Structural data for Pt(κ3–P1N1N2)(Y) and Pt(κ3–P1N1X1)(Y) (X1 = O1, C1, S1 or Se1), (Y = variable monodentate atoms/ligands) a.
ComplexSpace gr.
Cryst. cl.
Z		a [Å]
b [Å]
c [Å]		α[°]
β[°]
γ[°]		Chromophore
(Chelate Rings)
Ʈ4 b		Pt-L c
[Å]		L-Pt-L c
[°]		Ref.
REFCODE
A: Pt(κ3-P1N1N2)(Y)
[Pt{κ3-But2P(CH2)(C5H3N1). (CH2)N2Et2}(Cl)].C6H6
(at 120 K) 		tr
Pī
2		9.158(0)
10.963(0)
16.018(0)		77.29(0)
76.97(0)
69.11(0)		PtP1N1N2Cl
P1C2N1C2N2
0.044		P1 2.236(1)
N1 1.997(2)
N2 2.149(2)
Cl 2.296(2)		P1,N1 85.5 d
N1,N2 83.4 d
P1,N2 168.0
P1,Cl 98.5
N2,Cl 92.6
N1,Cl 176.0		[10]
WOGDAY
[Pt{κ3-Ph2P1(C7H5N1).
(C2H2O)N2C6H4OH)}(CH3)].
(CHCl3)
(at 150 K)		tr
Pī
2		9.917(1)
11.944(2)
14.872(2)		99.17(0)
103.82(0)
112.53(0) 		PtP1N1N2C
P1C3N1C2N2
0.032		P1 2.179(1)
N1 2.050(2)
N2 2.089(2)
H3C 2.045(2)		P1,N1 95.3 e
N1,N2 80.5 d
P1,N2 173.7
P1,C 89.0
N2,C 95.5
N1,C 174.7		[11]
GAJMOV
[Pt{κ3-Ph2P1(C7H5N1).
(C2H2O)N2(C6H4OH)}(CH3)].
1.5 toluene
(at 150 K)		m
P21/c
4		11.882(1)
14.184(1)
21.892(1)		103.75(0)PtP1N1N2C
P1C3N1C2N2
0.027		P1 2.184(2)
N1 2.061(3)
N2 2.075(3)
H3C 2.051(2)		P1,N1 95.4 e
N1,N2 81.0 d
P1,N2 176.4
P1,C 90.5
N2,C 93.0
N1,C 174.0		[11]
GAJMUB
[Pt{κ3-Ph2P1(C7H5N1).
(C3H6)N2(C7H5O2)}(CH3)].
2 toluene
(at 150 K)		m
P21/c
4		14.859(0)
15.607(0)
16.287(0)		95.88(0)PtP1N1N2C
P1C3N1C2N2
0.033		P1 2.189(1)
N1 2.077(2)
N2 2.070(2)
H3C 2.062(2)		P1,N1 95.2 e
N1,N2 80.3 d
P1,N2 175.4
P1,C 89.4
N2,C 94.9
N1,C 172.6		[11]
GAJNAI
[Pt{κ3-Ph2P1(C7H5N1)(C6H4)N2 (C10H9NO3)}(CH3)]Et2O
(at 150 K)		m
P21/c
4		10.992(0)
20.133(0)
16.933(0)		101.72(0)PtP1N1N2C
P1C3N1C2N2
0.040		P1 2.184(1)
N1 2.087(2)
N2 2.086(2)
H3C 2.062(2)		P1,N1 92.6 e
N1,N2 79.4 d
P1,N2 171.8
P1,C 91.5
N2,C 96.6
N1,C 173.7		[12]
QICYAD
[Pt{κ3-Ph2P1(C7H5N1)(C5H7O) N2(C10H10N2)}(CH3)]H2O
(at 93 K)		m
P21/c
4		8.739 (1)
14.988(2)
25.469(2)		 94.23(0)PtP1N1N2C
P1C3N1C2N2
0.052		P1 2.190(1)
N1 2.061(2)
N2 2.094(2)
H3C 2.083(2)		P1,N1 89.4 e
N1,N2 79.6 d
P1,N2 169.0
P1,C 92.2
N2,C 93.7
N1,C 172.1		[13]
DIYYIU
[Pt{κ3-Ph2P1(C7H5N1)(C2H2O)
N2(C6H4OH)}(CH3)]CHCl3
(at 150 K)		m
P21/c
4		10.191(0)
16.863(1)
17.525(1)		97.30(0)PtP1N1N2C
P1C3N1C2N2
0.030		P1 2.183(1)
N1 2.059(1)
N2 2.061(1)
H3C 2.055(1)		P1,N1 95.1 e
N1,N2 81.0 d
P1,N2 175.8
P1,C 91.2
N2,C 92.6
N1,C 173.4		[14]
CAJLAC
[Pt{κ3–Ph2P1(C7H6N1 = NCC1.
C5H6)}(Cl)]
(at 150 K)		tr
Pī
2		7.431(2)
10.031(3)
14.797(5)		101.10(0)
95.70(0)
98.76(0)		PtP1N1N2C
P1C3N1NCN2
0.038		P1 2.219(1)
N1 2.164(2)
N2 2.050(1)
Cl 2.297(2)		P1,N1 95.8 e
N1,N2 79.3 d
P1,N2 173.0
P1,Cl 90.8
N2,Cl 94.2
N1,Cl 173.4		[15]
XUYWEU
[Pt{κ3-Ph2P1(C7H5N1)(C7H8N)
(C7H8N2)}(Cl)]PF6		m
P21/c
4		18.910(3)
10.098(1)
19.429(3)		118.93(1)PtP1N1N2Cl
P1C3N1CN2
0.020		P1 2.234(1)
N1 2.120(1)
N2 2.104(1)
Cl 2.284(1)		P1,N1 93.3 e
N1,N2 85.6 d
P1,N2 178.7
P1,Cl 91.8
N2,Cl 89.2
N1,Cl 174.0		[16]
IFUQEF
B: Pt(κ3–P1N1O1)(Y)
[Pt{κ3-Ph2P1(C8H6N1)(N.
C7H5O1)}{κ1-Ph2P. (C15H13N2O)}].CH2Cl2
(at 200 K)		tr
Pī
2		12.614(2)
13.671(2)
15.754(3)		100.26(0)
99.33(0)
110.68(0)		PtP1N1O1P
P1C2N1NCO1
0.067		P1 2.233(2)
N1 1.985(2)
O1 2.050(2)
LP 2.261(1)		P1,N1 83.6 d
N1,O1 78.8 d
P1,O1 162.4
P1,P 102.9
O1,P 94.7
N1,Cl 173.3		[17]
EFODAE
[Pt{κ3-Ph2P1(C6H4N1).
(C7H4ClO1)}(P(p-tolyl3)]ClO4
(at 200 K)		m
P21/c
4		12.614(14)
20.280(20)
16.972(17)		 98.96(1)PtP1N1O1P
P1C2N1C3O1
0.028		P1 2.21(1)
N1 2.05(2)
O1 2.03(2)
LP 2.269(1)		P1,N1 82.7
N1,O1 91.2
P1,O1 172.1
P1,P 99.6
O1,P 86.5
N1,P 177.7		[18]
KAVZOX
[Pt{κ3-Ph2P1(C6H4N1).
(C8H7OO1)}
(Cl)]		m
P21/n
4		12.350(12)
12.138(14)
15.550(17)		97.70(1)PtP1N1O1Cl
P1C2N1C3O1
0.007		P1 2.195(1)
N1 2.005(2)
O1 2.080(2)
Cl 2.303(1)		P1,N1 83.6 d
N1,O1 92.3 e
P1,O1 178.5
P1,Cl 93.5
O1,Cl 87.9
N1,Cl 178.9		[18]
KAVZAJ
[Pt{κ3-Ph2P1(C6H4N1).
(C8H7OO1)}(I)](CH2Cl2)		m
P21/c
4		10.446(11)
16.389(17)
16.507(0)		100.241(1)PtP1N1O1I
P1C2N1C3O1
0.014		P1 2.207(1)
N1 2.011(2)
O1 2.045(2)
I 2.620(1)		P1,N1 84.8 d
N1,O1 91.9 e
P1,O1 176.6
P1,I 92.6
O1,I 89.2
N1,I 178.2		[18]
KAVZEN
[Pt{κ3-Ph2P1(C8H7N1O1)}(Cl)]or
Pna21
4		18.88(2)
13.10(1)
9.66(1)		 PtP1N1O1Cl
P1C3N1C3O1
0.027		P1 2.206(1)
N1 1.88(1)
O1 2.14(1)
Cl 2.386(4)		P1,N1 94.8(4) e
N1,O1 93.3(4) e
P1,O1 175.5
P1,Cl 89.1(2)
O1,Cl 84.0(2)
N1,Cl174.8		[19]
DERNIX
C: Pt(κ3–P1N1C1)(Y)
[Pt{κ3-Ph2P1(C7H6N1 = NC.
C1C5H6)}(Cl)]
(at 120 K)		m
P21/n
4		8.632(4)
17.191(8)
15.216(7)		96.3(0)PtP1N1C1Cl
P1C2N1NCC1
0.060		P1 2.291(2)
N1 1.972(2)
C1 2.023(2)
Cl 2.309(1)		P1,N1 85.2 d
N1,C1 78.7 d
P1,C1 163.9
P1,Cl 99.9
C1,Cl 84.0
N1,Cl174.6		[20]
YEHMOP
[Pt{κ3-Ph2P1(C7H5N1).
(C7H8C1)}(py)]BF4
(at 100 K)		m
P21
4		9.356(0)
19.892(1)
15.084(1)		90.76(0)PtP1N1C1N
P1C3N1C2C1
0.042		P1 2.292(1)
N1 2.000(2)
C1 2.035(2)
pyN 2.026(1)		P1,N1 92.1 e
N1,C1 82.3 d
P1,C1 174.3
P1,N 92.4
C1,N 93.6
N1,Cl170.7		[21]
NIVCAX
D: Pt(κ3–P1N1S1)(Y)
[Pt{κ3-Ph2P1(C6H4CHN1NC.
(S1)NHMe}(Cl)]		m
P21/c
4		14.695(6)
16.683(7)
19.297(9)		102.83(6)PtP1N1S1Cl
P1C3N1NCS1
0.022		P1 2.239(5)
N1 2.03(2)
S1 2.298(5)
Cl 2.304(5)		P1,N1 95.8(4) e
N1,S1 84.9(4) d
P1,S1 177.8(2)
P1,Cl 89.5(2)
S1,Cl 89.8(2)
N1,Cl174.4 (4)		[22]
HAFMOQ
[Pt{κ3-Ph2P1(C7H5N1)(MeS1). (But.NH2)}(I)]tr
Pī
2		10.529(1)
11.558(1)
14.550(1)		77.37(1)
84.45(1)
79.72(1)		PtP1N1S1I
P1C3N1C3S1
0.023		P1 2.240(2)
N1 2.056(6)
S1 2.363(2)
I 2.580(1)		P1,N1 89.1(1) e
N1,S1 93.2(1) e
P1,S1 176.2(2)
P1,I 93.6(2)
S1,I 84.2(2)
N1,I 175.4(2)		[23]
ROBHOP
E: Pt(κ3–P1N1Se1)(Cl)
[Pt{κ3-Ph2P1(C7H5N1).
(C3H6Se1)(Ph)}(Cl)]BF4
(at 150K)		m
P21/c
4		9.869(0)
23.847(0)
11.740(0)		99.65(0)PtP1N1Se1Cl
P1C3N1C3Se1
0.012		P1 2.407(14)
N1 2.028(4)
Se1 2.489(1)
Cl 2.308(1)		P1,N1 87.5(1) e
N1,Se1 95.7(1) e
P1,Se1 176.7(1)
P1,Cl 93.0(1)
Se1,Cl 83.7(1)
N1,Cl 178.8(1)		[24]
MULZIC
Footnotes: a Where more than one chemically equivalent distance or angle is present, the mean value is tabulated. The first number in parentheses is the e.s.d. and the second is the maximum deviation from the mean. b Parameter Ʈ4, degree of distortion. c The chemical identity of the coordinated atom ligand is specific in these columns. d Five-membered metallocyclic ring. e Six-membered metallocyclic ring.
Table 2. Data for Pt(κ3–X1P1X2)(Cl), Pt(κ3–P1S1Cl1)(Cl) and Pt(κ3–P1Si1N1)(OL) derivatives monodentate atoms/ligands) a.
Table 2. Data for Pt(κ3–X1P1X2)(Cl), Pt(κ3–P1S1Cl1)(Cl) and Pt(κ3–P1Si1N1)(OL) derivatives monodentate atoms/ligands) a.
ComplexSpace gr.
Cryst. cl.
Z		a [Å]
b [Å]
c [Å]		α [°]
β [°]
γ [°]		Chromophore
(Chelate Rings)
Ʈ4 b		Pt-L c
[Å]		L-Pt-L c
[°]		Ref.
REFCODE
[Pt{κ3-N1(C6H6)N(C6H10)N..
P1(Pri) (C6H6)N2}(Cl)].H2O
(at 150 K)		or
P212121
6		14.373(0)
9.906(0)
17.590(0)		 PtN1P1N2Cl
N1C2NP1NC2N2
0.032		N1 2.035
P1 2.187
N2 2.039
Cl 2.375		N1,P1 91.1 e
P1,N2 91.0 e
N1,N2 175.4
N1,Cl 90.4
N2,Cl 91.0
P1,Cl 173.0		[25]
IRAWOO
[Pt{κ3-PriS1(C6H4)P1.
(C6H4SPri) (C6H4)S2}(Cl)]
(at 123 K)		m
P21/n
4		8.790(0)
18.706(1)
15.508(1)		95.89(0)PtS1P1S2Cl
S1C2P1C2S2
0.055		S1 2.289
P1 2.189
S2 2.292
Cl 2.374		S1,P1 88.2 d
P1,S2 87.7 d
S1,S2 162.1
S1,Cl 93.0
S2,Cl 90.8
P1,Cl 178.3		[26]
EZORAO
[Pt{κ3-ButS1(C6H4)P1.
(C6H4SBut)(C6H4)S2}(Cl)].0.5CHCl3
(at 123 K)		m
P21/n
4		10.250(1)
18.715(2)
15.320(1)		96.65(0)PtS1P1S2Cl
S1C2P1C2S2
0.063		S1 2.287
P1 2.198
S2 2.297
Cl 2.360		S1,P1 88.7 d
P1,S2 88.8 d
S1,S2 158.7
N1,Cl 92.8
N2,Cl 90.8
P1,Cl 178.6		[26]
EZOQIV
[Pt{κ3-Ph2P1(C23H28S1). (B)(Ph2)Cl1)}(Cl)].2CH2Cl2
(at 123 K)		or
Pna21
4		21.373(0)
8.959(0)
25.330(3)		 PtP1S1Cl1Cl
P1C2S1C2BCl1
0.033		P1 2.212
S1 2.243
Cl1 2.391
Cl2 2.321		P1,S1 87.9 d
S1,Cl1 87.1 e
P1,Cl1 174.7
P1,Cl 93.4
Cl1,Cl 91.7
S1,Cl 173.3		[27]
DASMER
[Pt{κ3-cyh2P1(C6H4)Si1.
(CH3)(C7H6)N1(CH3)2)}.
(OSO2CF3)]
(at 123 K)		m
P21/c
4		19.851(1)
20.837(3)
15.443(2)		99.52(0)PtP1Si1N1O
P1C2Si1C3N1
0.033		P1 2.228
Si1 2.260
N1 2.177
LO 2.353		P1,Si1 85.8 d
Si1,N1 82.7 e
P1,N1 169.2
P1,O 95.0
N1,O 86.4
Si1,O 179.0		[28]
WUXFAI
Footnotes: a Where more than one chemically equivalent distance or angle is present, the mean value is tabulated. The first number in parentheses is the e.s.d. and the second is the maximum deviation from the mean. b Parameter Ʈ4, degree of distortion. c The chemical identity of the coordinated atom ligand is specific to these columns. d Six- membered metallocyclic ring. e Five-membered metallocyclic ring.
Table 3. Summary of metallocyclic rings, trans-L-Pt-L angles and parameter Ʈ4.
Table 3. Summary of metallocyclic rings, trans-L-Pt-L angles and parameter Ʈ4.
Metallocyclic Ringsα- L-Pt-L
[°]		β- L’-Pt-Y
[°]		Ʈ4
5 + 5—membered163.0176.20.058
6 + 5—membered172.9173.60.037
5 + 6—membered174.2177.50.023
6 + 6—membered176.5175.60.022
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Melník, M.; Mikuš, P. Heterotridentate Organomonophosphines in Pt(κ3–X1P1X2)(Y) (X1,2 = N1,2 or S1,2), Pt(κ3–P1N1X1)(Y) (X1 = O, C, S or Se) Pt(κ3–P1S1Cl1)(Cl) and Pt(κ3–P1Si1N1)(OL)—Structural Aspects. Crystals 2022, 12, 1772. https://doi.org/10.3390/cryst12121772

AMA Style

Melník M, Mikuš P. Heterotridentate Organomonophosphines in Pt(κ3–X1P1X2)(Y) (X1,2 = N1,2 or S1,2), Pt(κ3–P1N1X1)(Y) (X1 = O, C, S or Se) Pt(κ3–P1S1Cl1)(Cl) and Pt(κ3–P1Si1N1)(OL)—Structural Aspects. Crystals. 2022; 12(12):1772. https://doi.org/10.3390/cryst12121772

Chicago/Turabian Style

Melník, Milan, and Peter Mikuš. 2022. "Heterotridentate Organomonophosphines in Pt(κ3–X1P1X2)(Y) (X1,2 = N1,2 or S1,2), Pt(κ3–P1N1X1)(Y) (X1 = O, C, S or Se) Pt(κ3–P1S1Cl1)(Cl) and Pt(κ3–P1Si1N1)(OL)—Structural Aspects" Crystals 12, no. 12: 1772. https://doi.org/10.3390/cryst12121772

APA Style

Melník, M., & Mikuš, P. (2022). Heterotridentate Organomonophosphines in Pt(κ3–X1P1X2)(Y) (X1,2 = N1,2 or S1,2), Pt(κ3–P1N1X1)(Y) (X1 = O, C, S or Se) Pt(κ3–P1S1Cl1)(Cl) and Pt(κ3–P1Si1N1)(OL)—Structural Aspects. Crystals, 12(12), 1772. https://doi.org/10.3390/cryst12121772

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