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

Melník, Milan; Mikuš, Peter

doi:10.3390/cryst12121772

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Heterotridentate Organomonophosphines in Pt(κ³–X¹P¹X²)(Y) (X^1,2 = N^1,2 or S^1,2), 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.

Keywords:

structure; Pt(κ³–P¹X¹X²)(Y); Pt(κ³–X¹P¹X²)(Y); distortion; trans-influence

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–Bu^t₂P¹(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)(Bu^tNH₂)}(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–Bu^tS¹(C₆H₄)P¹(C₆H₄SBu^t)(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

Bu^t₂P¹(CH₂)(C₅H₃N¹)(CH₂)N²Et₂	(2-(di-t-butylphosphinomethyl)-6-diethyl-aminomethyl)pyridine)
Bu^tS¹(C₆H₄)P¹(C₆H₄SBu^t)(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)
m	monoclinic
N¹(C₆H₆)N(C₆H₁₀)NP¹(Prⁱ)(C₆H₆)N²	(2-isopropyl-1,3-bis(2-pyridylmethyl)-octahydro-1H-1,3,2-benzodiazophosphore
or	orthorhombic
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)(Bu^tNH₂)	(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)
py	pyridine
tr	triclinic

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Figure 1. Structure of [Pt{κ³–Ph₂P¹(C₇H₆N¹)(NC₅H₅N²)}(Cl)] [15].

Figure 2. Structure of [Pt{κ³–Ph₂P¹(C₇H₆N¹ = NCC¹C₅H₆)}(Cl)] [20].

Figure 3. Structure of [Pt{κ³–PrⁱS¹(C₆H₄)P¹(C₆H₄SPrⁱ)(C₆H₄)S²}(Cl)] [26].

Figure 4. Structure of Pt{κ³–Ph₂P¹(C₂₃H₂₈S¹)(B)(Ph₂)Cl¹}(Cl)] [27].

Figure 5. Structure of [Pt{κ³–cyh₂P¹(C₆H₄)Si¹(CH₃)(C₇H₆)N¹(CH₃)₂}(OSO₂CF₃)] [28].

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.

Complex	Space 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-Bu^t₂P(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). (Bu^t.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.

Complex	Space 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-Bu^tS¹(C₆H₄)P¹. (C₆H₄SBu^t)(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.

Metallocyclic Rings	α- L-Pt-L [°]	β- L’-Pt-Y [°]	Ʈ₄
5 + 5—membered	163.0	176.2	0.058
6 + 5—membered	172.9	173.6	0.037
5 + 6—membered	174.2	177.5	0.023
6 + 6—membered	176.5	175.6	0.022

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Melník, M.; Mikuš, P. Heterotridentate Organomonophosphines in Pt(κ³–X¹P¹X²)(Y) (X^1,2 = N^1,2 or S^1,2), 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

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Melník M, Mikuš P. Heterotridentate Organomonophosphines in Pt(κ³–X¹P¹X²)(Y) (X^1,2 = N^1,2 or S^1,2), 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

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Melník, Milan, and Peter Mikuš. 2022. "Heterotridentate Organomonophosphines in Pt(κ³–X¹P¹X²)(Y) (X^1,2 = N^1,2 or S^1,2), 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

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Heterotridentate Organomonophosphines in Pt(κ³–X¹P¹X²)(Y) (X^1,2 = N^1,2 or S^1,2), Pt(κ³–P¹N¹X¹)(Y) (X¹ = O, C, S or Se) Pt(κ³–P¹S¹Cl¹)(Cl) and Pt(κ³–P¹Si¹N¹)(OL)—Structural Aspects

Abstract

1. Introduction