Polyhedral oxaplatinaborane chemistry: characterisation of [9,9-(PMe2Ph)2-arachno-9,6-PtOB8H10] and its metallaborane non-oxa cognate [6,6-(PMe2Ph)2-arachno-6-PtB9H11-9-(PMe2Ph)]

Kim, Young‐Hee; Brownless, Annette; Cooke, Paul; Greatrex, Robert; Kennedy, John D.; Pett, Mark Thornton

doi:10.1016/s1387-7003(98)00005-7

Cited by 22 publications

(19 citation statements)

References 23 publications

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“…The V1–V2 bond length in compound 6 (2.7589(10) Å) is slightly shorter than that in [(CpV) 2 (B 2 H 6 ) 2 ] 10. The boron–oxygen bond length (1.502(8) Å) is comparable with that in other oxametallaboranes, for example 1.508(9) Å in [9,9‐(PMe 2 Ph) 2 ‐ arachno ‐9,6‐PtOB 8 H 10 ]34 and 1.521(6) Å in [7‐(Cp*)‐10‐(NEt 3 )‐ nido ‐7,12‐RhOB 10 H 10 ] 35. The V–O distances (1.972(5) and 1.975(4) Å) are longer than those in dinuclear μ‐oxo‐divanadium(III) cluster [V 2 O(O 2 CC 2 H 5 ) 2 ‐ (HB(pz) 3 ) 2 ]36 (1.781(5) and 1.774(5) Å; pz=pyrazole).…”

Section: Resultsmentioning

confidence: 87%

“…Structural comparison of clusters 2 and 4-6: Structurally characterized polyhedral heteroborane clusters that contain oxygen as a cluster constituent with a cluster connectivity of three are very rare. [37] Until now, few of these types are known, they are: nido-[(h 6 -C 6 H 3 Me 3 )FeOB 8 H 10 ], [38] arachno-[(PMe 2 Ph) 2 PtOB 8 H 10 ], [34] nido-[Cp*RhOB 10 H 10 A C H T U N G T R E N N U N G (NEt 3 )], [27,35] nido-[Cp*RhOB 10 H 9 ClA C H T U N G T R E N N U N G (PMe 2 Ph)], [27,31] [(Cp*Mo) 2 B 5 (m 3 -OEt)H 6 R (R= H, nBuO), [39] and [(Cp*Ta) 2 B 4 H 10 O]. [24] The oxavanadaborane cluster species of type 6, which has an oxygen atom in an open-face position, is unprecedented and, to the best of our knowledge, this is the first oxavanadaborane to be reported.…”

Section: Synthesis and Characterization Of Oxavanadaborane 6 And Vanamentioning

confidence: 99%

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Synthesis and Structural Characterization of New Divanada‐ and Diniobaboranes Containing Chalcogen Atoms

Roy

Bose

Geetharani

et al. 2012

Chemistry A European J

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The reaction of [Cp(n)MCl(4-x)] (M=V: n=2, x=2; M=Nb: n=1, x=0; Cp=η(5)-C(5) H(5)) with LiBH(4)⋅THF followed by thermolysis in the presence of dichalcogenide ligands E(2)R(2) (E=S, Te; R=2,6-(tBu)(2)-C(6)H(2)OH, Ph) and 2-mercaptobenzothiazole (C(7)H(5)NS(2)) yielded dimetallaheteroboranes [{CpV(μ-TePh)}(2)(μ(3) -Te)BH⋅thf] (1), [(CpV)(2)(BH(3)S)(2)] (2), [(CpNb)(2)B(4)H(10)S] (3), [(CpNb)(2)B(4)H(11)S(tBu)(2)C(6)H(2)OH] (4), and [(CpNb)(2)B(4)H(11)TePh] (5). In cluster 1, the V(2)BTe atoms define a tetrahedral framework in which the boron atom is linked to a THF molecule. Compound 2 can be described as a dimetallathiaborane that is built from two edge-fused V(2)BS tetrahedron clusters. Cluster 3 can be considered as an edge-fused cluster in which a trigonal-bipyramidal unit (Nb(2)B(2)S) has been fused with a tetrahedral core (Nb(2)B(2)) by means of a common Nb(2) edge. In addition, thermolysis of an in-situ-generated intermediate that was produced from the reaction of [Cp(2)VCl(2)] and LiBH(4)⋅THF with excess BH(3)⋅THF yielded oxavanadaborane [(CpV)(2)B(3)H(8)(μ(3)-OEt)] (6) and divanadaborane cluster [(CpV)(2)B(5)H(11)] (7). Cluster 7 exhibits a nido geometry with C(2v) symmetry and it is isostructural with [(Cp*M)(2)B(5)H(9+n)] (M=Cr, Mo, and W, n=0; M=Ta, n=2; Cp*=η(5)-C(5)Me(5)). All of these new compounds have been characterized by (1)H NMR, (11)B NMR, and (13)C NMR spectroscopy and elemental analysis and the structural types were established unequivocally by crystallographic analysis of compounds 1-4, 6, and 7.

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Section: Resultsmentioning

confidence: 87%

Section: Synthesis and Characterization Of Oxavanadaborane 6 And Vanamentioning

confidence: 99%

Synthesis and Structural Characterization of New Divanada‐ and Diniobaboranes Containing Chalcogen Atoms

Roy

Bose

Geetharani

et al. 2012

Chemistry A European J

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“…The molecular frameworks of all these compounds are formally derived from an icosahedron by the removal of two vertices, with the structures corresponding to that expected for a 13 skeletaleelectron-pair (sep) arachnocluster with 10 vertices. Interestingly, the metallaboranes [6,6-(PMe 2 Ph) 2 -9-(PMe 2 Ph)-MB 9 H 11 ], where M ¼ Pt or Pd [47,48], and platinathiaboranes [8-OEt-9,9-(PPh 3 ) 2 -9,6-PtSB 8 H 10 ] and [9,9-(PPh 3 ) 2 -9,6-PtSB 8 H 10 ] [49], have 12 sep's that correspond to 10-vertex nido-structures. Formally, the 10-vertex boat-type cage is obtained by the removal of the vertex of connectivity six of an octadodecahedron and, therefore, the WilliamseWade cluster geometry and electron-counting approach predicts the same 10-vertex cluster geometry for frameworks with 12 or 13 sep's [50,51].…”

Section: Resultsmentioning

confidence: 99%

Synthesis and characterization of new 10- and 12-vertex CO-ligated metallathiaboranes

Luaces

Bould

Macı́as

et al. 2012

Journal of Organometallic Chemistry

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Dedicated to Professor Thomas P. Fehlner on his 75th birthday. He has been a superb mentor of many scientists around the world working on "inorganometallic chemistry". Keywords:The reaction between [arachno-6-SB 9 H 12 ] À and [IrCl(CO)(PMe 3 ) 2 ] affords the previously reported 11-vertex cluster, [8,8,(PMe 3 ) 2 -arachno-8,7-IrSB 9 H 10 ] (4), and small amounts of the new 10-vertex iridathiaborane [9,9,9,(H)(PMe 3 ) 2 -arachno-9,6-IrSB 8 H 10 ] (5). Alternatively, a rational synthesis of iridathiadecaboranes is effected from the reaction of the 9-vertex anion [arachno-4-SB 8 H 11 ] À with [MCl(CO)(PPh 3 ) 2 ], to afford new CO-ligated 10-vertex metallathiaboranes of formulation, [9,9,9,(H)(PPh 3 ) 2 -arachno-9,6-MSB 8 H 10 ], where M ¼ Rh (6) and Ir (7), in useful yields of 61% and 60% respectively. Treatment of the 11-vertex rhodathiaborane, [8,8-(PPh 3 ) 2 -8,7-nido-RhSB 9 H 10 ] (1) with nBuLi, followed by addition of [IrCl(CO)(PMe 3 ) 2 ] affords the 12-vertex iridarhodathiaborane, [1,2-(m-CO)-1,1,2-(PMe 3 ) 3 -2-(PPh 3 )-closo-1,2-IrRhSB 9 H 9 ] (8) in low yield (0.7%). The 10-vertex metallathiaboranes, 5, 6 and 7, and the bimetallic 12-vertex cluster, 8, have been characterized by multinuclear NMR spectroscopy. In addition, the molecular structures of compounds 5, 6, and 8 have been studied by X-ray diffraction.

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“…These are [(PPh 3 ) 2 -arachno-PtSB 8 H 10 ], [19] the platinazaborane [(PPh 3 ) 2 -arachno-NPtB 8 H 11 ] [20] and the platinoxaborane [(PPh 3 ) 2 -arachno-OPtB 8 H 10 ]. [21] The rhodathiaborane [6,6, -ion, features a pseudo-squareplanar rhodium vertex that reacts with Lewis bases such as CO, pyridine and PR 3 .…”

Section: X-ray Diffraction Analysis Of 1-4mentioning

confidence: 99%

Reversible Small‐Molecule Interactions with Coordinatively Unsaturated Metal Centers Held in Metallathiaborane Clusters

et al. 2017

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Polyhedral oxaplatinaborane chemistry: characterisation of [9,9-(PMe2Ph)2-arachno-9,6-PtOB8H10] and its metallaborane non-oxa cognate [6,6-(PMe2Ph)2-arachno-6-PtB9H11-9-(PMe2Ph)]

Cited by 22 publications

References 23 publications

Synthesis and Structural Characterization of New Divanada‐ and Diniobaboranes Containing Chalcogen Atoms

Synthesis and Structural Characterization of New Divanada‐ and Diniobaboranes Containing Chalcogen Atoms

Synthesis and characterization of new 10- and 12-vertex CO-ligated metallathiaboranes

Reversible Small‐Molecule Interactions with Coordinatively Unsaturated Metal Centers Held in Metallathiaborane Clusters

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