Chloro-rhodaboratrane [(Cp∗Rh)(L2)BCl] 4 has been synthesized from rhodium N,S-heterocyclic carbene complex [(Cp∗Rh)(L2)(1-benzothiazol-2-ylidene)], 1, (L = C7H4NS2) and borane reagent BHCl2.SMe2. The Rh-B bond in 4 is buttressed between two benzothiazolyl units in [3.3.0] fashion. The presence of B-Cl bond allowed us to explore the chemistry of boratrane 4 at the boron centre. The reaction of ethynylmagnesium bromide with 4 yielded η1-vinyl complex [Cp∗RhBr(C2H2)L] 5, containing a five membered metallaheterocycle. In an objective to abstract the chloride, alike borylene synthesis from haloboryl, we performed the reaction of 4 with NaBArF4 that resulted the thiolato bridged bimetallic compound [Cp∗Rh(μ-L)3RhCp∗][BArF4] 6 (ArF: C6H3(CF3)2-3,5). © 2016 Elsevier B.V. All rights reserved.

Sundargopal Ghosh

Department Of Chemistry

Kuppusamy Yuvaraj

boron

Chlorine

Organic compounds

Rhodium

Synthesis (chemical)

BENZOTHIAZOLYL

BIMETALLIC COMPOUND

BORANE REAGENTS

BORATRANE

BORYLENES

Carbenes

Heterocyclic carbene complexes

VINYL COMPLEXES

Rhodium compounds

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IIT Madras

Journal of Organometallic Chemistry

The chemistry of ruthenium–borane complex, [Cp∗RuCO(μ-H)BH2L] (Cp∗ = η5-C5Me5; L = C7H4NS2), 1 with various alkynes has been explored. Photolysis of 1 with alkynyl-Grignard, [HC[tbnd]CMgBr] in toluene led to the isolation of vinyl hydroborate complex [Cp∗Ru(μ-H)BH{HC[dbnd]CH2}L], 2a as a sole product. Compound 2a can be viewed as a ruthenium–borate complex with an ethylene moiety. Further, the chemistry of 1 with various internal and terminal alkynes has been performed in photolytic conditions. Photolysis of 1 with [RC[tbnd]CR] (R = CO2Me) yielded vinyl hydroborate complex [Cp∗Ru(μ-H)BCl{RC[dbnd]CR}L], 2b. Terminal alkynes [HC[tbnd]CR] (R = Ph or CO2Me) under the same reaction conditions led to the isolation of metal vinyl complexes [Cp∗Ru(CO)(C2HR)(L)], 3a and 3b (3a: R = Ph; 3b: R = CO2Me). In addition, DFT calculations were carried out to analyze the bonding and electronic structures of these new compounds. © 2017 Elsevier Ltd

Fulltext

Polyhedron

Chemistry of ruthenium σ-borane complex, [Cp∗RuCO(μ-H)BH2L] (Cp∗ = η5-C5Me5; L = C7H4NS2) with terminal and internal alkynes: Structural characterization of vinyl hydroborate and vinyl complexes of ruthenium

Treatment of [M2(μ-Cl)2(cod)2] (M=Ir and Rh) with Na[H2B(bt)2] (cod=1,5-cyclooctadiene and bt=2-mercaptobenzothiazolyl) at low temperature led to the formation of dimetallaheterocycles [(Mcod)2(bt)2], 1 and 2 (1: M=Ir and 2: M=Rh) and a borate complex [Rh(cod){κ2-S,S′-H2B(bt)2}], 3. Compounds 1 and 2 are structurally characterized metal analogues of 1,5-cyclooctadiene. Metal–metal bond distances of 3.6195(9) Å in 1 and 3.6749(9) Å in 2 are too long to consider as bonding. In an attempt to generate the Ru analogue of 1 and 2, that is [(Rucod)2(bt)2], we have carried out the reaction of [Ru(Cl)2(cod)(CH3CN)2] with Na[H2B(bt)2]. Interestingly, the reaction yielded agostic complexes [Ru(cod)L{κ3-H,S,S′-H2B(bt)2}], 4 and 5 (4: L=Cl; 5: L=C7H4NS2). One of the key differences between 4 and 5 is the presence of different ancillary ligands at the metal center. The natural bond orbital (NBO) analysis of 1 and 2 shows that there is four lone pairs of electrons on each metal center with a significant amount of d character. Furthermore, the electronic structures and the bonding of these complexes have been established on the ground of quantum-chemical calculations. All of the new compounds were characterized by IR,1H,11B,13C NMR spectroscopy, and X-ray crystallographic analysis. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Chemistry - A European Journal

Reactivity of [M2(μ-Cl)2(cod)2] (M=Ir, Rh) and [Ru(Cl)2(cod)(CH3CN)2] with Na[H2B(bt)2]: Formation of Agostic versus Borate Complexes

A neutral metallaborane comprising a Rh4B12 polyhedron with icosioctahedron geometry with 16 vertices and 28 triangular faces was prepared (see structure; Rh: red, B: green). The cage has the shape of a 12-membered truncated tetrahedron with four capped hexagonal faces. © 2013 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.

Angewandte Chemie - International Edition

Boron beyond the icosahedral barrier: A 16-vertex metallaborane

The reaction of [CpnMCl4-x] (M=V: n=2, x=2; M=Nb: n=1, x=0; Cp=Î·5-C5H5) with LiBH4·THF followed by thermolysis in the presence of dichalcogenide ligands E2R2 (E=S, Te; R=2,6-(tBu) 2-C6H2OH, Ph) and 2-mercaptobenzothiazole (C7H5NS2) yielded dimetallaheteroboranes [{CpV(μ-TePh)}2(μ3-Te)BH·thf] (1), [(CpV)2(BH3S)2] (2), [(CpNb)2B 4H10S] (3), [(CpNb)2B4H 11S(tBu)2C6H2OH] (4), and [(CpNb)2B4H11TePh] (5). In cluster 1, the V2BTe 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 V2BS tetrahedron clusters. Cluster 3 can be considered as an edge-fused cluster in which a trigonal-bipyramidal unit (Nb2B2S) has been fused with a tetrahedral core (Nb2B2) by means of a common Nb2 edge. In addition, thermolysis of an in-situ-generated intermediate that was produced from the reaction of [Cp2VCl2] and LiBH 4·THF with excess BH3·THF yielded oxavanadaborane [(CpV)2B3H8(μ3- OEt)] (6) and divanadaborane cluster [(CpV)2B5H 11] (7). Cluster 7 exhibits a nido geometry with C2v symmetry and it is isostructural with [(Cp*M)2B 5H9+n] (M=Cr, Mo, and W, n=0; M=Ta, n=2; Cp*=Î·5-C5Me5). All of these new compounds have been characterized by 1H NMR, 11B NMR, and 13C NMR spectroscopy and elemental analysis and the structural types were established unequivocally by crystallographic analysis of compounds 1-4, 6, and 7. Group 5 alive: Divanadatellura- and divanadathiaboranes were obtained from the treatment of Group 5 metal polychlorides with dichalcogenides and monoboranes. The treatment of [Cp2VCl2] with monoboranes yielded an oxavanadaborane and a divanadaborane (see structures). Copyright © 2012 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.

Synthesis and structural characterization of new divanada- and diniobaboranes containing chalcogen atoms

Dalton Trans.

Borate-based ligands with two soft heterocycle/thione groups and their sodium and bismuth complexes

Reaction of [Cp*TaCl4] (Cp* = η5- C5Me5) with a sixfold excess of LiBH4· thf followed by BH3·thf in toluene at 100°C led to the isolation of hydrogen-rich metallaboranes [(Cp*Ta)2B 4H10] (1), [(Cp*Ta)2B5H 11] (2), [(Cp*Ta)2B5H10) (C6H4CH3)] (3), and [(Cp*TaCl) 2B5H11] (4) in modest yield. Compounds 1-3 are air- and moisture-sensitive but 4 is reasonably stable in air. Their structures are predicted by the electron-counting rules to be a bicapped tetrahedron (1), bicapped trigonal bipyramids (2, 3), and a nido structure based on a closo dodecahedron (4). Yellow tantalaborane 1 has a nido geometry with C2v symmetry and is isostructural with [(Cp*M)2B4H 8] (M = Cr and Re); whereas 2 and 3 are C3v-symmetric and isostructural with [(Cp*M)2B5H9] (M = Cr, Mo, W) and [(Cp*ReH)2B5Cl5]. The most remarkable feature of 4 is the presence of a hydride ligand bridging the ditantalum center to form a symmetrical tantalaborane cluster with a long Ta-Ta bond (3.22 Å). Cluster 4 is a rare example of electronically unsaturated metallaborane containing four TaHB bonds. All these new metallaboranes have been characterized by mass spectrometry, 1H, 11B, and 13C NMR spectroscopy, and elemental analysis, and the structural types were unequivocally established by crystallographic analysis of 1-4. © 2008 Wiley-VCH Verlag GmbH &amp; Co. KGaA.

Metallaboranes of the early transition metals: Direct synthesis and characterization of [{(η5-C5Me5)Ta} 2BnHm] (n=4, m = 10; n = 5, m = 11), [{(η5-C5Me5)Ta}2B 5H10(C6H4CH3)]

Angewandte Chemie International Edition

Palladium Complexes of N-Heterocyclic Carbenes as Catalysts for Cross-Coupling Reactions—A Synthetic Chemist's Perspective

Chemistry of Rh-N,S heterocyclic carbene complexes

Journal	Data powered by TypesetJournal of Organometallic Chemistry
Publisher	Data powered by TypesetElsevier B.V.
ISSN	0022328X
Open Access	No