An Efficient Route to Group 6 and 8 Metallaborane Compounds: Synthesis of arachno‐[Cp*Fe(CO)B3H8] and closo‐[(Cp*M)2B5H9] (M = Mo, W)

Geetharani, K.; Bose, Shubhankar Kumar; Pramanik, Goutam; Saha, Tanmoy; Ramkumar, V.; Ghosh, Sundargopal

doi:10.1002/ejic.200801137

Cited by 59 publications

(23 citation statements)

References 78 publications

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“…Thus, they provide a platform for the evaluation of electronic compatibility or incompatibility of metal and borane fragments. One of the most studied and explored cluster systems in metallaborane chemistry is the M 2 B 5 system reported by us [23][24][25][26][27][28][29][30][31][32][33] and others [34][35][36][37][38][39][40][41]. Earlier, Fehlner and co-workers showed an attractive route for the synthesis of electronically unsaturated metallaboranes, i.e., those, which are formally electron deficient with respect to the number of skeletal electron pairs (sep), required to maintain the observed molecular geometry [34][35][36]42,43].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structures and Chemistry of the Metallaboranes of Group 4–9 with M2B5 Core Having a Cross Cluster M–M Bond

et al. 2019

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In an attempt to expand the library of M2B5 bicapped trigonal-bipyramidal clusters with different transition metals, we explored the chemistry of [Cp*WCl4] with metal carbonyls that enabled us to isolate a series of mixed-metal tungstaboranes with an M2{B4M’} {M = W; M’ = Cr(CO)4, Mo(CO)4, W(CO)4} core. The reaction of in situ generated intermediate, obtained from the low temperature reaction of [Cp*WCl4] with an excess of [LiBH4·thf], followed by thermolysis with [M(CO)5·thf] (M = Cr, Mo and W) led to the isolation of the tungstaboranes [(Cp*W)2B4H8M(CO)4], 1–3 (1: M = Cr; 2: M = Mo; 3: M = W). In an attempt to replace one of the BH—vertices in M2B5 with other group metal carbonyls, we performed the reaction with [Fe2(CO)9] that led to the isolation of [(Cp*W)2B4H8Fe(CO)3], 4, where Fe(CO)3 replaces a {BH} core unit instead of the {BH} capped vertex. Further, the reaction of [Cp*MoCl4] and [Cr(CO)5·thf] yielded the mixed-metal molybdaborane cluster [(Cp*Mo)2B4H8Cr(CO)4], 5, thereby completing the series with the missing chromium analogue. With 56 cluster valence electrons (cve), all the compounds obey the cluster electron counting rules. Compounds 1–5 are analogues to the parent [(Cp*M)2B5H9] (M= Mo and W) that seem to have generated by the replacement of one {BH} vertex from [(Cp*W)2B5H9] or [(Cp*Mo)2B5H9] (in case of 5). All of the compounds have been characterized by various spectroscopic analyses and single crystal X-ray diffraction studies.

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Section: Introductionmentioning

confidence: 99%

Synthesis, Structures and Chemistry of the Metallaboranes of Group 4–9 with M2B5 Core Having a Cross Cluster M–M Bond

et al. 2019

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“…[1] The development of metallaborane chemistry has followed a similar pathway, with new species often obtained from conditions that favor the thermodynamic product, either through thermolysis or by simple metathesis reactions between a preformed polyborane anion and transition-metal halides. [2][3][4][5] Detailed investigations of the Co, [6] Rh, [7] Ir, [8,9] Fe, [10] Ru, [11] Re, [12,13] Cr, [14,15] Mo, [10,[16][17][18] W, [10,19,20] and Ta [21][22][23] systems reported to date reveal that metal identity affects products. For example, the earlier transition metals facilitate dehydrogenation leading to highly condensed clusters, such as closo-A C H T U N G -T R E N N U N G [(Cp*M) 2 B n H n + m ], (M = Re: [13] n = 7-10, m = 0; M = W: [12] n = 7, m = 2), whereas late transition elements form stable nido-or arachno-metallaboranes, such as nido-[(Cp*Ru) 2 B 10 H 16 ] [24] or arachno-1-[(Cp*IrH)B 4 H 9 ].…”

Section: Introductionmentioning

confidence: 99%

Fine Tuning of Metallaborane Geometries: Chemistry of Metallaboranes of Early Transition Metals Derived from Metal Halides and Monoborane Reagents

Bose

Geetharani

Ramkumar

et al. 2009

Chemistry A European J

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Reaction of [Cp(n)MCl(4-x)] (M=V: n=x=2; M=Nb: n=1, x=0) or [Cp*TaCl(4)] (Cp=eta(5)-C(5)H(5), Cp*=eta(5)-C(5)Me(5)), with [LiBH(4).thf] at -70 degrees C followed by thermolysis at 85 degrees C in the presence of [BH(3).thf] yielded the hydrogen-rich metallaboranes [(CpM)(2)(B(2)H(6))(2)] (1: M=V; 2: M=Nb) and [(Cp*Ta)(2)(B(2)H(6))(2)] (3) in modest to high yields. Complexes 1 and 3 are the first structurally characterized compounds with a metal-metal bond bridged by two hexahydroborate (B(2)H(6)) groups forming a symmetrical complex. Addition of [BH(3).thf] to 3 results in formation of a metallaborane [(Cp*Ta)(2)B(4)H(8)(mu-BH(4))] (4) containing a tetrahydroborate ligand, [BH(4)](-), bound exo to the bicapped tetrahedral cage [(Cp*Ta)(2)B(4)H(8)] by two Ta-H-B bridge bonds. The interesting structural feature of 4 is the coordination of the bridging tetrahydroborate group, which has two B-H bonds coordinated to the tantalum atoms. All these new metallaboranes have been characterized by mass, (1)H, (11)B, and (13)C NMR spectroscopy and elemental analysis and the structural types were established unequivocally by crystallographic analysis of 1-4.

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“…The composition and structure of 2 is established in comparison of the spectroscopic data with arachno-[CpÃFe(CO)B 3 H 8 ] [15] and related species [22][23][24][25]. The composition of 2 is defined by the mass, an isotopic distribution pattern characteristic of one Fe, two B and one Se atom.…”

Section: Arachno-[cpfe(co)b 2 H 4 (L-seph)] (2)mentioning

confidence: 99%

“…Accordingly, in our continuing search for different metal precursors, containing CpÃM (CpÃ = g 5 -C 5 Me 5 ) fragment, we found that mono(halo)(cyclopentadienyl)metal carbonyl, [CpÃM(CO) n X], (when M = Mo or W, X = Cl and n = 3; M = Fe, X = I and n = 2), are very useful to group 6 and 8 metallaboranes [15]. After it had been discovered that the reaction of [CpÃMoCl 4 ] with [LiBH 4 Áthf] in presence of dichalcogenide ligands yielded a new class of open-cage dimolybdaheteroborane clusters [16], an investigation of metallaheterobaranes containing group 8 metal, became of interest.…”

Section: Introductionmentioning

confidence: 98%

A new entry into ferraborane chemistry: Synthesis and characterization of heteroferraborane complexes

Geetharani

Bose

Basak

et al. 2011

Inorganica Chimica Acta

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An Efficient Route to Group 6 and 8 Metallaborane Compounds: Synthesis of arachno‐[CpFe(CO)B₃H₈] and closo‐[(CpM)₂B₅H₉] (M = Mo, W)

Cited by 59 publications

References 78 publications

Synthesis, Structures and Chemistry of the Metallaboranes of Group 4–9 with M2B5 Core Having a Cross Cluster M–M Bond

Synthesis, Structures and Chemistry of the Metallaboranes of Group 4–9 with M2B5 Core Having a Cross Cluster M–M Bond

Fine Tuning of Metallaborane Geometries: Chemistry of Metallaboranes of Early Transition Metals Derived from Metal Halides and Monoborane Reagents

A new entry into ferraborane chemistry: Synthesis and characterization of heteroferraborane complexes

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