Unusual Open Eight-Vertex Oxamolybdaboranes: Structural Characterizations of (η5-C5Me5Mo)2B5(μ3-OEt)H6R (R = H andn-BuO)

Sahoo, Satyanarayan; Dhayal, Rajendra S.; Varghese, Babu; Ghosh, Sundargopal

doi:10.1021/om801065r

Cited by 51 publications

(37 citation statements)

References 38 publications

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“…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%

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: 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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“…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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“…Since the discovery of various borylene complexes, the chemistry of this sub-area of transition-metal complexes of boron has received significant attention, both from structure/bonding and reactivity perspectives. [6][7][8][9][10] Recently, we synthesized a variety of transition-metalÀboron complexes [11][12][13] and, in doing so, we reported the synthesis of numerous bridged borylene complexes, [8] one of which has been successfully employed in the generation of vinyl borylenes. [14] To provide a more-general access to borylene complexes of different metals, we planned to synthesize bridged borylene complexes with other transition metals.…”

Section: Introductionmentioning

confidence: 99%

New Heteronuclear Bridged Borylene Complexes That Were Derived from [{Cp*CoCl}₂] and Mono‐MetalCarbonyl Fragments

Sharmila

Yuvaraj

Barik

et al. 2013

Chemistry A European J

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The synthesis, structural characterization, and reactivity of new bridged borylene complexes are reported. The reaction of [{Cp*CoCl}2] with LiBH4·THF at -70 °C, followed by treatment with [M(CO)3(MeCN)3] (M=W, Mo, and Cr) under mild conditions, yielded heteronuclear triply bridged borylene complexes, [(μ3-BH)(Cp*Co)2(μ-CO)M(CO)5] (1-3; 1: M=W, 2: M=Mo, 3: M=Cr). During the syntheses of complexes 1-3, capped-octahedral cluster [(Cp*Co)2(μ-H)(BH)4{Co(CO)2}] (4) was also isolated in good yield. Complexes 1-3 are isoelectronic and isostructural to [(μ3-BH)(Cp*RuCO)2(μ-CO){Fe(CO)3}] (5) and [(μ3-BH)(Cp*RuCO)2(μ-H)(μ-CO){Mn(CO)3}] (6), with a trigonal-pyramidal geometry in which the μ3-BH ligand occupies the apical vertex. To test the reactivity of these borylene complexes towards bis-phosphine ligands, the room-temperature photolysis of complexes 1-3, 5, 6, and [{(μ3-BH)(Cp*Ru)Fe(CO)3}2(μ-CO)] (7) was carried out. Most of these complexes led to decomposition, although photolysis of complex 7 with [Ph2P(CH2)(n)PPh2] (n=1-3) yielded complexes 9-11, [3,4-(Ph2P(CH2)(n)PPh2)-closo-1,2,3,4-Ru2Fe2(BH)2] (9: n=1, 10: n=2, 11: n=3). Quantum-chemical calculations by using DFT methods were carried out on compounds 1-3 and 9-11 and showed reasonable agreement with the experimentally obtained structural parameters, that is, large HOMO-LUMO gaps, in accordance with the high stabilities of these complexes, and NMR chemical shifts that accurately reflected the experimentally observed resonances. All of the new compounds were characterized in solution by using mass spectrometry, IR spectroscopy, and (1)H, (13)C, and (11)B NMR spectroscopy and their structural types were unequivocally established by crystallographic analysis of complexes 1, 2, 4, 9, and 10.

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Unusual Open Eight-Vertex Oxamolybdaboranes: Structural Characterizations of (η⁵-C₅Me₅Mo)₂B₅(μ₃-OEt)H₆R (R = H andn-BuO)

Cited by 51 publications

References 38 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, Structures and Chemistry of the Metallaboranes of Group 4–9 with M2B5 Core Having a Cross Cluster M–M Bond

New Heteronuclear Bridged Borylene Complexes That Were Derived from [{Cp*CoCl}₂] and Mono‐MetalCarbonyl Fragments

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Unusual Open Eight-Vertex Oxamolybdaboranes: Structural Characterizations of (η5-C5Me5Mo)2B5(μ3-OEt)H6R (R = H andn-BuO)

Cited by 51 publications

References 38 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, Structures and Chemistry of the Metallaboranes of Group 4–9 with M2B5 Core Having a Cross Cluster M–M Bond

New Heteronuclear Bridged Borylene Complexes That Were Derived from [{Cp*CoCl}2] and Mono‐MetalCarbonyl Fragments

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Unusual Open Eight-Vertex Oxamolybdaboranes: Structural Characterizations of (η⁵-C₅Me₅Mo)₂B₅(μ₃-OEt)H₆R (R = H andn-BuO)

New Heteronuclear Bridged Borylene Complexes That Were Derived from [{Cp*CoCl}₂] and Mono‐MetalCarbonyl Fragments