Metal atom syntheses of metallaboron clusters. 2. Synthesis of cobaltathiaborane and cobaltadithiaborane complexes. Crystal and molecular structures of 2,3,6-(.eta.-C5H5)2Co2SB5H7 and 7,6,8-(.eta.-C5H5)CoS2B6H8

Zimmerman, George J.; Sneddon, Larry G.

doi:10.1021/ja00395a019

Cited by 29 publications

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“…[10] The non-bonded distance between the S1 and S2 atoms of 3.258 is similar to the analogous sulfur-rich cluster (NH 4 ) 2 [(S 2 ) 2 Mo(S 2 ) 2 ]·2 H 2 O [18] and the average B-S distance is comparable to that in [(CpCo) 2 B 2 S 2 H 2 ]. [19,20,21] The average V-S distance of 2.343 in compound 2 is similar to…”

Section: Resultsmentioning

confidence: 53%

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: 53%

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 proximity of the heteroatoms and the metal centers in the metallacarborane and metallathiaborane products implies that the metal is intimately involved in the process although similar reactions of non-metal-containing borane clusters allow other possibilities. Examples include the classical reaction of C 2 H 2 with L 2 B 10 H 12 to form C 2 B 10 H 12 , the addition of nitriles to SB 9 H 11 to afford monocarbon heteroborane species, and the synthesis of cobaltathiaboranes from H 2 S in a metal atom vapor reactor …”

Section: Resultsmentioning

confidence: 99%

“…Syntheses of metallaheteroborane clusters are typically effected by the addition of metal complexes to heteroborane clusters , aza, and other heteroatom species, but herein we focus only on those containing the atoms C, S, and N. Little attention has been given to the idea of producing metallaheteroborane clusters by the addition of the heteroatom to metallaborane clusters. Some carbon insertion products involving iridaboranes have been isolated in low yields as the unexpected degradation products from the reaction of Ir(CO)Cl(PPh 3 ) 2 and [B 10 H 10 ] 2- in refluxing methanol, viz .…”

Section: Introductionmentioning

confidence: 99%

Metallaborane Heteroatom Incorporation Reactions: Metallacarboranes, Metallathiaboranes, and an Iridaazaborane from Iridanonaborane Precursors

1996

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Formation of metallaheteroboranes by insertion of heteroatoms into an existing metallaborane cluster, rather than adding the metal moiety to the heteroborane which is normally the case, has been achieved in the cases of carbon, nitrogen, and sulfur to produce nine-, ten-, and eleven-vertex metallaheteroborane clusters. Thus passage of acetylene through refluxing p-xylene solutions of either arachno-[(PMe3)2(CO)HIrB8H12] (1a) or nido-[(PMe3)2(CO)IrB8H11] (2a) afforded the 11-vertex cluster nido-[9,9,9-(PMe3)2(CO)-9,7,8-IrC2B8H11] (5a) in up to 44% yield. With the cage substituted species arachno-[(PMe3)2(CO)HIrB8H11Cl] (1b), the analogous product is nido-[5-Cl-9,9,9-(PMe3)2(CO)-9,7,8-IrC2B8H10] (5b) and the position of the Cl substituent in the product suggests that the acetylene moiety attacks across the open face of the intermediate nido-iridanonaborane species and that cage rearrangement does not occur during the course of the reaction. Similarly, reaction of 1a with H2S under identical conditions results in the formation nido-[2,2,2-(PMe3)2H-2,6-IrSB8H10] (9a), closo-[2,2,2-(PMe3)2H-2,1-IrSB8H8] (10), and nido-[(PMe3)2HIrS2B8H8] (11a) in overall yields of 13%, 7%, and 20%, respectively. Additionally, refluxing a solution of 1a and anhydrous hydrazine in xylene afforded a 10% yield of the novel iridaazanonaborane nido-[2,2,2-(PMe3)3-2,9-IrNB7H9] (12). The compound is the first metallaazanonaborane cluster to be described, and its formation indicates that methods similar to those used to generate azaboranes may be used on metallaboranes to generate metallazaboranes. In addition to characterization by a combination of 1H, 31P, and 11B NMR and IR spectroscopy and high-resolution mass spectrometry, single-crystal X-ray diffraction studies were carried out on compounds 5a, 9a, 10, and 12.

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“…*H{11B) NMR (C6D6, 200 MHz), (relative intensity, assignment): 4.54 (2, BH), 4. 30 (2, BH), 2.48 (6, CH2), 1.41 (2, BH), 0.66 (9, CH3), -1.67 (1, BHB), -4.60 (2, BHB).…”

Section: Methodsmentioning

confidence: 99%

Structural characterization and cage-condensation reactions of the coupled-cage borane 1:2'-[B5H8]2: new routes to higher single-cage boranes and carboranes

Briguglio¹,

Carroll²,

Corcoran³

et al. 1986

Inorg. Chem.

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Rh-S-H are -14.5°in 2). Thus, the hydrogens linked to one metal and to one sulfur remain in close proximity.A CH2C12 solution of 2 under a stream of argon loses 2 mol of H2 (as determined by GC) and transforms into [(triphos)Rh-(M-S)2Rh(triphos)](BPh4)2 (3) (31P|'H| NMR (CD3COCD3, 293 K) 24.02 ppm (/(P-Rh) = 102 Hz, doublet, triphos)). Brown crystals are precipitated by addition of ethanol. A stream of H2 turns a solution of 3 to the original pink color, and the complex 2 is obtained quantitatively in 4 h. A preliminary X-ray analysis on 3 has confirmed the structural formulation given in Scheme I.The ability of 3 to activate homodinuclear molecules shows up in the reaction with oxygen. When 02 is bubbled throughout a CH2C12 solution of 3, red crystals of the µ-SO complex [(triphos)Rh(/u-SO)2Rh(triphos)](BPh4)2 (4) are obtained quantitatively. The crystal structure and characterization of 4, prepared by a different synthetic strategy, have recently been reported by (3) Ghilardi, C.

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Metal atom syntheses of metallaboron clusters. 2. Synthesis of cobaltathiaborane and cobaltadithiaborane complexes. Crystal and molecular structures of 2,3,6-(.eta.-C5H5)2Co2SB5H7 and 7,6,8-(.eta.-C5H5)CoS2B6H8

Cited by 29 publications

References 0 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

Metallaborane Heteroatom Incorporation Reactions: Metallacarboranes, Metallathiaboranes, and an Iridaazaborane from Iridanonaborane Precursors

Structural characterization and cage-condensation reactions of the coupled-cage borane 1:2'-[B5H8]2: new routes to higher single-cage boranes and carboranes

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