An Unusual Conversion of Paramagnetic [3-Cl-3,3,8-{Ph₂P(CH₂)_nPPh-µ-(C₆H₄-ortho)}-1,2-(CH₃)₂-closo-3,1,2-Ru^IIIC₂B₉H₈] (n = 3 and 4) to Form the First 18-Electron P-Phenylene ortho-Cycloboronated closo-Ruthenacarboranes with a Dioxygen Ligand

1. Introduction

Boron-containing transition metal clusters exhibiting ortho-cycloboronation of the phosphine or diphosphine ligands on a metal atom are long known in metallaborane [1,2,3] and monocarbon metallacarborane [4,5] chemistry. However, first examples of related 12-vertex dicarbon metallacarborane complexes were reported only recently [6,7,8,9,10,11], and all known complexes of these series are Ru^III species having a 17-electron shell. In this regard it is of interest that these paramagnetic ortho-cycloboronated metallacarborane systems demonstrate the exceptionally high efficiency as catalyst precursors for the atom transfer radical polymerization (ATRP) of methyl methacrylate, as well as of other vinyl monomers [7,8,9,10,11,12,13,14]. On the other hand, such electron-deficient complexes hold considerable promise in a variety of ways for the development of ruthenacarborane chemistry. We now report an initial study on the reactivity of paramagnetic ortho-phenylenecycloboronated closo-ruthenacarboranes resulting in preparation of a short series of new dioxygen ruthenium-carborane complexes.

2. Results and Discussion

Polyhedral contraction reactions of transition metals metallacarboranes occurring under base-mediated conditions to produce smaller metallacarborane species have not been extensively reported [15,16,17,18]. Hence, we proposed to extend studies in this area starting from the previously untested ortho-cycloboronated P-phenylene paramagnetic species [3-Cl-3,3,8-[Ph₂P(CH₂)_nPPh-µ-( H₈] (1,2-dimethyl-3-chloro-3,8-µ-{ortho-[phenyl-(3'-diphenylphosphinopropyl-κP(Ru))phosphino]phenyl-P(Ru),C¹(B⁸)}-1,2-dicarba-3-ruthena-closo-dodecaborane (1) n = 3 [7] and 1,2-dimethyl-3-chloro-3,8-μ-{ortho-[phenyl-(4'-diphenylphosphinobutyl-κP(Ru))phosphino]phenyl-P(Ru),C¹(B⁸)}-1,2-dicarba-3-ruthena-closo-dodecaborane (2); n = 4 [9]) with the hope of preparing either ortho-cycloboronated 11-vertex {RuC₂B₈} complexes or smaller clusters of these series. Accordingly, we examined the reaction of 1 and 2 with a fourfold molar excess of KOH at room temperature in a 1:1 benzene/methanol mixture in air.

Only ruthenacarborane products were isolated from these reactions, each in ca. 45% yield, after column chromatography on silica gel. These species proved, however, to exhibit different structures from those anticipated. It was evident from crystallographic data that the isolated species are actually novel 18-electron diamagnetic closo-ruthenacarboranes with the dioxygen ligand at the metal vertex, viz., [3-(η²-O₂)-3,3,8-[Ph₂P(CH₂)_nPPh-µ-( H₈] (3, n = 3; 4, n = 4), respectively (Scheme 1).

Scheme 1. Schematic representation of the reactions of 1 and 2 with an oxygen.

Scheme 1. Schematic representation of the reactions of 1 and 2 with an oxygen.

Single-crystal X-ray diffraction studies were carried out on both species 3 and 4. Their selected bond distances and angles are summarized in Table 1. Figure 1, on the top, shows the molecular structure of complex 3. In the crystal of complex 4, there are two independent molecules, which show only small differences in their geometry (see Table 1), and the molecular structure of only one of them is therefore shown in Figure 1, on the bottom.

Table 1. Selected bond lengths (Å) and angles (deg.) in 3 and 4 (two independent molecules A and B).

Compound	3	4
		A	B
Ru(3)-O(1)	2.037(2)	2.036(3)	2.015(3)
Ru(3)-O(2)	2.040(2)	2.041(3)	2.043(3)
Ru(3)-P(1)	2.3412(7)	2.3580(13)	2.3693(13)
Ru(3)-P(2)	2.2928(7)	2.3201(13)	2.3280(13)
Ru(3)-C(1)	2.320(3)	2.316(5)	2.318(5)
Ru(3)-C(2)	2.336(3)	2.356(5)	2.338(4)
Ru(3)-B(4)	2.251(3)	2.255(5)	2.282(5)
Ru(3)-B(7)	2.251(3)	2.258(5)	2.290(6)
Ru(3)-B(8)	2.253(3)	2.259(5)	2.274(5)
O(1)-O(2)	1.403(3)	1.399(4)	1.404(4)
C(1)-C(2)	1.621(4)	1.633(7)	1.640(6)
O(1)-Ru(3)-O(2)	40.26(8)	40.14(12)	40.49(12)
O(1)-Ru(3)-P(2)	109.21(6)	112.24(10)	115.91(10)
O(2)-Ru(3)-P(2)	79.80(6)	81.07(10)	83.70(9)
O(1)-Ru(3)-P(1)	75.32(6)	74.19(9)	74.10(9)
O(2)-Ru(3)-P(1)	100.35(6)	98.09(10)	95.59(10)
P(2)-Ru(3)-P(1)	86.76(3)	89.17(4)	86.97(5)
O(2)-O(1)-Ru(3)	69.97(11)	69.76(18)	68.68(18)
O(1)-O(2)-Ru(3)	69.77(11)	70.10(18)	70.82(18)

Table 1. Selected bond lengths (Å) and angles (deg.) in 3 and 4 (two independent molecules A and B).

Compound	3	4
		A	B
Ru(3)-O(1)	2.037(2)	2.036(3)	2.015(3)
Ru(3)-O(2)	2.040(2)	2.041(3)	2.043(3)
Ru(3)-P(1)	2.3412(7)	2.3580(13)	2.3693(13)
Ru(3)-P(2)	2.2928(7)	2.3201(13)	2.3280(13)
Ru(3)-C(1)	2.320(3)	2.316(5)	2.318(5)
Ru(3)-C(2)	2.336(3)	2.356(5)	2.338(4)
Ru(3)-B(4)	2.251(3)	2.255(5)	2.282(5)
Ru(3)-B(7)	2.251(3)	2.258(5)	2.290(6)
Ru(3)-B(8)	2.253(3)	2.259(5)	2.274(5)
O(1)-O(2)	1.403(3)	1.399(4)	1.404(4)
C(1)-C(2)	1.621(4)	1.633(7)	1.640(6)
O(1)-Ru(3)-O(2)	40.26(8)	40.14(12)	40.49(12)
O(1)-Ru(3)-P(2)	109.21(6)	112.24(10)	115.91(10)
O(2)-Ru(3)-P(2)	79.80(6)	81.07(10)	83.70(9)
O(1)-Ru(3)-P(1)	75.32(6)	74.19(9)	74.10(9)
O(2)-Ru(3)-P(1)	100.35(6)	98.09(10)	95.59(10)
P(2)-Ru(3)-P(1)	86.76(3)	89.17(4)	86.97(5)
O(2)-O(1)-Ru(3)	69.97(11)	69.76(18)	68.68(18)
O(1)-O(2)-Ru(3)	69.77(11)	70.10(18)	70.82(18)

According to the crystallographic data, the ruthenium atom in both 3 and 4 is bound in a η⁵-fashion to the C₂B₃ open face of C,C'-dimethylated nido-{C₂B₉}-carborane cage ligands, which have ortho-phenylenecycloboronated linkages connecting one of the P-phenyl rings of the ruthenium-bound dppp or dppb ligand, respectively, to the cluster B(8) atom. As expected, the presence of ortho-cycloboronated bridging fragment in both 3 and 4 accounts for the observed differences in the Ru-P(1) and Ru-P(2) bond lengths (2.3412(7) and 2.2928(7) Å in 3; av. 2.3637(13) and 2.3241(13) Å in 4), respectively. In addition, the metal atom in both structures 3 and 4 is coordinated by the dioxygen ligand in almost symmetrical η²-fashion with Ru-O distances range 2.015(3)-2.043(3) Å (av. 2.035 Å). The O-O distance in 3 (1.403(3) Å) and in 4 (1.399(4), 1.404(4) Å) is comparable to those found in the known oxygen Cp* ruthenium complexes such as [Cp*Ru(O₂)(dppe)]PF₆ (1.398(5)) Å [19]) or [Cp*Ru(O₂)(dppm)]BPh₄ (1.37(1)) Å [20], however, is somewhat shorter as compared with that in the only structurally studied oxygen iridium-carborane species with the exo-polyhedrally bound metal atom, [(Ph₃P)₂IrO₂(7,8-(MeS)₂-7,8-C₂B₉H₁₀)]•Me₂CO (1.471(8) Å) [21]. The carborane C-C bond distances in 3 (1.621(4) Å) and 4 (1.633(7) and 1.640(6) Å), as well as the other cluster C-B (1.69–1.75 Å) and B-B (1.73–1.84 Å) connectivities, are typical of 12-vertex closo-metallacarboranes [22].

Figure 1. ORTEP representation of the molecular structures of complexes 3 (top) and 4 (bottom) with thermal ellipsoids at the 50% probability level. Hydrogen atoms are omitted for clarity.

Figure 1. ORTEP representation of the molecular structures of complexes 3 (top) and 4 (bottom) with thermal ellipsoids at the 50% probability level. Hydrogen atoms are omitted for clarity.

Analytical, IR and NMR spectroscopic data are entirely consistent with the formulation of complexes 3 and 4 made based on the above X-ray diffraction experiments. The Nujol mull infrared spectra of 3 and 4 show a broad band at ca. 940 cm⁻¹. Since no such bands were observed in the IR spectra of starting complexes 1 and 2, these bands in IR spectra of 3 and 4 were assigned to ν_O-O. The detailed examination of the ¹H, ¹³C{¹H}, and ³¹P{¹H} NMR spectra of complexes 3 and 4 provided additional useful information on their structures. The ³¹P{¹H} NMR spectra of complexes 3 and 4 each contains two resonances: two sharp doublets (δ_P(1) = 18.6 ppm, δ_P(2) = 52.9; J_P(1)-P(2) = 75.3 Hz) for 3; one broadened and one sharp doublet (δ_P(1) = 23.0 ppm, δ_P(2) = 64.8; J_P(1)-P(2) = 65.0 Hz) for 4. The low-field phosphorus resonances at δ 52.9 and 64.8 ppm were tentatively assigned to the “PPh-µ-(C₆H₄-ortho)” moiety of 3 and 4, which is connected to boron atom of the cage ligand. The ¹H-NMR spectra of 3 and 4, along with the resonances derived from the phenyl protons of the dppp and dppb ligands at δ between ca. 7.8 and 6.8 ppm, as well as the resonances of the cage CH₃ protons (δ, 1.14, 0.81 for 3 and δ, 1.09, 0.64 ppm for 4), are indicative of a set of non-equivalent protons of three and four methylene groups attributable to the chelating diphosphine ligands. The latter sets proved to be the only structurally significant and are particularly diagnostic of the presence the ortho-phenylenecycloboronated moiety in 3 and 4. Therefore, we strictly assigned all these resonances by the use of ¹H{³¹P}, ¹³C{¹H} NMR, as well as 2D [13C-1H]-HSQC correlation spectra. Thus, the fully ³¹P-decoupled ¹H{³¹P} NMR spectra of 3 and 4 each revealed two pairs of apparently simplified 1H multiplet resonances originating from diphosphine CH₂ groups substituted by the PPh₂ functions. In agreement with this, in the 2D [13C-1H]-HSQC spectrum of 3 (Figure 2, on the left) each pair of these 1H multiplets are connected by cross-peaks to one of the two carbon resonances that appear as doublet of doublets at δ 24.4 and 26.7 ppm with ca. J_C,P = 35.3 and J_C,P = 7.5 Hz. Similar cross-peaks between each pairs of 1H multiplets, which are susceptible to ³¹P-decoupling, a broadened doublet at δ 30.8 ppm and a sharp doublet at 25.3 ppm both having ca. same J_C,P = 32.0 Hz can be observed in the 2D [¹³C-¹H]-HSQC spectrum of 4 (Figure 2, on the right). The differences in the multiplicity observed for the carbon resonances derived from “Ph₂P₍₁₎CH₂(CH₂)_nCH₂P₍₂₎Ph-µ-(C₆H₄-ortho)” units in the ¹³C{¹H} NMR spectra of 3 and 4 can be explained by a shorter carbon chain in the case of diphosphine ligand of 3, which results in additional splitting of resonances derived from CH₂ groups on the far-located ³¹P nucleus.

Figure 2. [¹H-¹³C] HSQC spectrum for 3 (on the left) and 4 (on the right) in CD₂Cl₂ solution at 25 °C showing the assignment of the proton resonances.

Figure 2. [¹H-¹³C] HSQC spectrum for 3 (on the left) and 4 (on the right) in CD₂Cl₂ solution at 25 °C showing the assignment of the proton resonances.

3. Experimental

3.1. General Information

Starting complexes 1 [7] and 2 [9] were prepared according to the published procedures. Chromatography columns (ca. 15 cm in length and 3.5 cm in diameter) packed with silica gel (Acros, Geel, Belgium, 0.035–0.070 mm, 60 A) were used for purification of the prodacts 3 and 4. The ¹H, ³¹P{¹H}, ¹³C{¹H}, ¹¹B/¹¹B{¹H} and correlation NMR spectra were obtained with a Bruker AMX-400 spectrometer (¹H, 400.13 MHz; ³¹P, 161.98 MHz; ¹³C, 100.61 MHz; ¹¹B, 128.33 MHz) using TMS as an internal reference and 85% H₃PO₄ and BF₃•Et₂O as the external references, respectively. IR spectra were obtained from nujol mull on a Nicolet Magna-750 spectrometer. Microanalyses were performed by Analytical Laboratory of the Institute of Organoelement Compounds of the RAS.

3.2. Preparation of [3-(η²-O₂)-3,3,8-[Ph₂P(CH₂)₃PPh-µ-( H₈] (3)

A mixture of 1 (113 mg, 0.16 mmol) and an excess of crushed KOH (45 mg, 0.804 mmol) in a 1:1 benzene-methanol mixture (20 mL) was stirred at ambient temperature (~10 min) until all starting material was dissolved and the color of the solution changes from deep red to pale yellow. The flask was opened on air, and the reaction mixture was allowed to stir additionally for 1 h. Solvent was evaporated under reduced pressure and the residue was dissolved in benzene (8–10 mL), filtered and treated by column chromatography on silica gel. The brownish band was eluted from the column using benzene, the solvent was removed, and the resultant solid was re-crystallized from a n-hexane-benzene mixture, affording 50.8 mg (45.2% yield) of pure complex 3 as brown crystals. Anal. Calcd for C₃₁H₃₉B₉O₂P₂Ru: C, 52.89%, H, 5.58%, B, 13.82%. Found: C, 52.82%, H, 5.56%, B, 13.70%. IR (Nujol mull, cm⁻¹): ν_O-O 941 (w). ¹H-NMR (CD₂Cl₂, 20 °C) δ 7.68 to 6.92 [set of seven m. 19H, Ph₂P₍₁₎(CH₂)₃P₍₂₎Ph-µ-(C₆H₄-ortho)], 3.01, 2.46 [each m, 1H, Ph₂P₍₁₎CH₂CH₂CH₂P₍₂₎Ph-µ-(C₆H₄-ortho)], 2.90, 2.76 (each m, 1H, Ph₂P₍₁₎CH₂CH₂CH₂P₍₂₎Ph-µ-(C₆H₄-ortho)), 2.38, 1.49 [td and m, 1H, Ph₂P₍₁₎CH₂CH₂CH₂P₍₂₎Ph-µ-(C₆H₄-ortho)], 1.60 (s, H₂O in the solvent), 1.14, 0.81 (each s, 3H, CH₃-carb). ³¹P{¹H}-NMR (CD₂Cl₂, 20 °C,) δ 52.9 (d, 1P, J_P,P = 75.3 Hz), 18.5 (d, 1P, J_P,P = 75.3 Hz). ¹³C{¹H}-NMR (CD₂Cl₂, 20 °C) δ 139.1, 138.7, 135.5, 128.7 (each d, J_C,P = 58.4, 58.7, 54.4, 48.6 Hz, C_ipso), 134.8 (br. s), 134.1 (d, J_C,P = 6.7 Hz), 134.0 (d, J_C,P = 20.0 Hz), 132.2, 130.7, 130.3, 130.2 (each d, J_C,P = 2.0, 2.7, 2.2, 2.7 Hz, C_para), 131.2 (d, J_C,P = 7.6 Hz), 128.3 (d, J_C,P = 10.8 Hz), 127.8 (d, J_C,P = 9.9 Hz), 127.6 (d, J_C,P = 9.4 Hz), 126.7 (d, J_C,P = 8.6 Hz), 75.6 (br. d-like, C_carb), 75.2 (br. d-like, C_carb), 29.7 (s, Me), 26.7 (dd, J_C,P = 35.0, 7.0 Hz, CH₂P₍₁₎Ph₂), 24.4 [dd, J_C,P = 35.7, 8.1 Hz, CH₂P₍₂₎Ph-µ(C₆H₄-ortho)], 24.1 (s, Me), 18.3 (s, PCH₂CH₂CH₂P). ¹¹B{¹H} NMR (CD₂Cl₂, 20 °C): 17.2 (s, 1B), −1.8 (3B), −3.0 (1B), −4.0 (1B), −7.9 (3B).

3.3. Preparation of [3-(η²-O₂)-3,3,8-[Ph₂P(CH₂)₄PPh-µ-( H₈] (4)

The procedure was carried out as for 3: starting complex 1 (45 mg, 0.062 mmol), KOH (17 mg, 0.304 mmol), 1:1 benzene-methanol mixture (10 mL), 10 min + 1 h under air. After isolation and purification via column chromatography on silica gel, the product was then re-crystallized from n-hexane–benzene, affording 20.5 mg (45.8% yield) of pure complex 4 as brownish-yellow crystals. IR (Nujol mull, cm⁻¹): ν_O-O 938 (w). Anal. Calcd for C₃₂H₄₁B₉O₂P₂Ru•C₆H₆: C, 57.33%, H, 5.95%. Found: C, 57.62%, H, 6.13%. ¹H-NMR (CD₂Cl₂, 20 °C, J, Hz):, 7.8–6.9 [set of eight overlapped m. 19H, Ph₂P₍₁₎(CH₂)₄P₍₂₎Ph-µ-(C₆H₄-ortho)], 3.35, 2.37 (m and q-like, 1H, Ph₂P₍₁₎CH₂CH₂CH₂CH₂P₍₂₎Ph-µ-(C₆H₄-ortho)), 2.97, 2.63 (q-like and t-like, 1H, Ph₂P₍₁₎CH₂CH₂CH₂CH₂P₍₂₎Ph-µ-(C₆H₄-ortho)), 2.05, 1.92, 1.63, 1.27 (each m, 1H, Ph₂P₍₁₎CH₂CH₂CH₂CH₂P₍₂₎Ph-µ-(C₆H₄-ortho)), 1.09, 0.64 (each s, 3H, Me). ³¹P{¹H}-NMR (CD₂Cl₂, 20 °C, J, Hz): 64.7 (d, br, 1P, J_P,P = 65.0 Hz), 22.9 (d, 1P, J_P,P = 65.0 Hz). ¹³C{¹H}-NMR (CD₂Cl₂) δ 140.2 (d, J = 54.0 Hz, C_ipso), 139.5, 138.9 (overlapping d, J_C,P = 51.3, 58.0 Hz, C_ipso), 134.3 (d, J_C,P = 5.1 Hz), 133.5 (d, J_C,P = 20.4 Hz), 131.8, 130.7, 130.2, 130.0 (each d, J_C,P = 2.1, 2.1, 2.6, 2.6 Hz, C_para), 130.9 (d, J_C,P = 7.4 Hz), 129.6 (d, J_C,P = 41.9 Hz, C_ipso), 129.0 (d, J_C,P = 4.1 Hz), 128.3 (d, J_C,P = 9.5 Hz), 127.7 (d, J_C,P = 9.5 Hz), 126.7 (d, J_C,P = 8.1 Hz), 76.4–75.8 (m, C_carb), 30.9 (br. d, J_C,P = 32.9 Hz, CH₂P₍₂₎Ph-µ-(C₆H₄-ortho)), 25.4 (d, J_C,P = 31.2 Hz, CH₂P₍₁₎Ph₂), 24.3, 20.0 (each s, PCH₂CH₂CH₂CH₂P), 24.2, 20.1 (each s, Me). ¹¹B{¹H} NMR (CD₂Cl₂, 20 °C): 17.5 (s, 1B, B(8)), −1.0 (2B), −2.1 (1B), −3.9 (1B), −6.9 (2B), −7.8 (1B), −10.0 (1B).

3.4. X-ray Structure Determination for Complexes 3 and 4

Single-crystal X-ray diffraction study was carried out with a Bruker SMART 1000 [23] for 3 and Bruker SMART APEX II [24] for 4 diffractometers (graphite monochromated Mo-K_α radiation, λ = 0.71073 Å, ω-scan technique). The SHELXTL software [25] was used for space group and structure determination, refinements, graphics, and structure reporting. The structures were solved by direct methods and refined by the full-matrix least-squares technique against F² with the anisotropic thermal parameters for all non-hydrogen atoms. The hydrogen atoms of carborane moieties were located from difference Fourier maps, the rest hydrogen atoms were placed in the geometrically calculated positions. All hydrogen atoms were included in the structure factors calculations in the riding motion approximation. In the crystal structure of 4, the central atom C (16B) of dppb ligand in the one of two independent molecules is disordered over two positions with 0.8/0.2 occupancies. In both structures 3 and 4, the CH₂Cl₂ solvent molecules are presented. The principal experimental and crystallographic parameters are listed in Table 2. CCDC 992977 (for 3) and 992978 (for 4) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html (or from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44 1223 336033; E-mail: deposit@ccdc.cam.ac.uk).

Table 2. Crystal data, data collection and structure refinement parameters for 3 and 4.

Compound	3	4
Molecular formula	C31H39B9O2P2Ru•2(CH2Cl2)	C32H41B9O2P2Ru•0.25(CH2Cl2)
Formula weight	873.77	739.18
Dimension, mm3	0.20 × 0.15 × 0.10	0.28 × 0.14 × 0.07
Crystal system	triclinic	triclinic
Temperature, K	120	100
Space group	P?1	P?1
a, Å	9.791(2)	10.361(2)
b, Å	10.063(4)	16.496(4)
c, Å	20.831(1)	21.721(5)
α, deg.	82.764(1)	76.958(4)
β, deg.	84.678(1)	81.790(4)
γ, deg.	62.696(1)	79.194(4)
V, Å3	1894.6(1)	3533(1)
Z	2	4
ρcalc, g·cm−3	1.532	1.390
2 θmax, deg.	60	54
Linear absorption ( µ), cm−1	8.13	7.95
No. unique refl. ( Rint)	10975 (0.0306)	15322 (0.1018)
No. observed refl. ( I > 2σ(I))	8254	8960
No. parameters	470	877
R1 (on F for observed refl.) a	0.0456	0.0534
wR2 (on F2 for all refl.) b	0.1017	0.1197
GOOF	0.980	0.907

Note: ^a R₁ = Σ||F_o − |F_c||/Σ|F_o|; ^b wR₂ = {Σ[w(F_o² − F_c²)²]/Σw(F_o²)²}^1/2.

Table 2. Crystal data, data collection and structure refinement parameters for 3 and 4.

Compound	3	4
Molecular formula	C31H39B9O2P2Ru•2(CH2Cl2)	C32H41B9O2P2Ru•0.25(CH2Cl2)
Formula weight	873.77	739.18
Dimension, mm3	0.20 × 0.15 × 0.10	0.28 × 0.14 × 0.07
Crystal system	triclinic	triclinic
Temperature, K	120	100
Space group	P?1	P?1
a, Å	9.791(2)	10.361(2)
b, Å	10.063(4)	16.496(4)
c, Å	20.831(1)	21.721(5)
α, deg.	82.764(1)	76.958(4)
β, deg.	84.678(1)	81.790(4)
γ, deg.	62.696(1)	79.194(4)
V, Å3	1894.6(1)	3533(1)
Z	2	4
ρcalc, g·cm−3	1.532	1.390
2 θmax, deg.	60	54
Linear absorption ( µ), cm−1	8.13	7.95
No. unique refl. ( Rint)	10975 (0.0306)	15322 (0.1018)
No. observed refl. ( I > 2σ(I))	8254	8960
No. parameters	470	877
R1 (on F for observed refl.) a	0.0456	0.0534
wR2 (on F2 for all refl.) b	0.1017	0.1197
GOOF	0.980	0.907

Note: ^a R₁ = Σ||F_o − |F_c||/Σ|F_o|; ^b wR₂ = {Σ[w(F_o² − F_c²)²]/Σw(F_o²)²}^1/2.

4. Conclusions

The complexes described in this paper are novel oxygen-containing ortho-phenylenecycloboronated closo-ruthenacarboranes of the general formula [3-(η²-O₂)-3,3,8-[Ph₂P(CH₂)_nPPh-µ-( H₈] (3, n = 3) and (4, n = 4). They were prepared by a facile and potentially useful method starting from paramagnetic species [3-Cl-3,3,8-{Ph₂P(CH₂)_nPPh-µ-( H₈] (n = 3 and 4), which formally undergo a mild base-mediated chlorine-oxygen displacement reaction. Based on these and the literature data, it is envisaged that suitably constituted paramagnetic ruthenacarborane complexes as the potential precursors might open up extensive applications in cluster ruthenacarborane chemistry as well as in the homogeneous metallacarborane catalysis.