Metallaheteroborane clusters of group 5 transition metals derived from dichalcogenide ligands

Bose, Shubhankar Kumar; Mobin, Shaikh M.; Ghosh, Sundargopal

doi:10.1016/j.jorganchem.2011.06.040

Cited by 26 publications

(11 citation statements)

References 37 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Alternatively, the structure of 3 can be viewed as a pentagonal bipyramid with two missing equatorial connectivities. The Nb1–Nb2 bond length (2.8044(5) Å) is shorter than that observed in [(CpNb) 2 (B 2 H 6 ) 2 ] (2.9477(16) Å)10 and in other niobaborane clusters 8b. The shortening of the Nb–Nb bond might have arisen from the effect of the sulfur atom, which withdraws electron density from the cluster.…”

Section: Resultsmentioning

confidence: 69%

“…As shown in Scheme , clusters 2, 4 , and the proposed [(CpV) 2 (BH 3 Se) 2 ] ( I ) have six skeletal‐electron pairs and 44 cluster valence electrons. Although the reaction of [Cp 2 VCl 2 ] with LiBH 4 ⋅ THF in the presence of diphenyl diselenide possibly produces compound I , its spectroscopic simplicity and our inability to produce it led us to isolate organovanadium selenido cluster [{CpV(μ‐SePh)} 2 (μ‐Se)] by the concurrent loss of boranes 8b. A proposed rationale for hypothetical cluster I is based on the observed electron counts of divanadaheteroborane clusters 2 and 4 – 6 .…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

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

Roy

Bose

Geetharani

et al. 2012

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Section: Resultsmentioning

confidence: 69%

Section: Resultsmentioning

confidence: 99%

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

Roy

Bose

Geetharani

et al. 2012

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

“…Complexes with chalcogenide ligands include divanadium and polyvanadium clusters as well as oxovanadium complexes having monochalcogen and dichalcogen ligands. Structures 06, 07, and 08 (Herberhold et al, 124 Bolinger et al 125 ) have long V−V distances (3.11 126 Rheingold, 127,128 Bose et al 129,130 ). Complexes 15 to 19 present longer V−V separations of about 2.80 Å, 131−134 while structure 20 with a V 2 Se 4 moiety has a R MM value of 2.779 Å close to this range (Ibers 135 ).…”

Section: Divanadaboranes and Complexes With Chalcogen Ligandsmentioning

confidence: 99%

Metal–Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc

2018

View full text Add to dashboard Cite

This survey of metal–metal (MM) bond distances in binuclear complexes of the first row 3d-block elements reviews experimental and computational research on a wide range of such systems. The metals surveyed are titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and zinc, representing the only comprehensive presentation of such results to date. Factors impacting MM bond lengths that are discussed here include (a) the formal MM bond order, (b) size of the metal ion present in the bimetallic core (M2) n+, (c) the metal oxidation state, (d) effects of ligand basicity, coordination mode and number, and (e) steric effects of bulky ligands. Correlations between experimental and computational findings are examined wherever possible, often yielding good agreement for MM bond lengths. The formal bond order provides a key basis for assessing experimental and computationally derived MM bond lengths. The effects of change in the metal upon MM bond length ranges in binuclear complexes suggest trends for single, double, triple, and quadruple MM bonds which are related to the available information on metal atomic radii. It emerges that while specific factors for a limited range of complexes are found to have their expected impact in many cases, the assessment of the net effect of these factors is challenging. The combination of experimental and computational results leads us to propose for the first time the ranges and “best” estimates for MM bond distances of all types (Ti–Ti through Zn–Zn, single through quintuple).

show abstract

“…For example, nido ‐rhodathiaborane [8,8,8‐(PPh 3 ) 2 H‐9‐(NC 5 H 5 )‐ nido ‐8,7‐RhSB 9 H 9 ] acts as a catalyst for the isomerization and hydrogenation of alkenes. [8c] Although metallaheteroboranes comprised of thia, , , and aza[4b] ligands have been explored, compounds that contain heavier heteroatoms, such as selenolato and tellurolato ligands, are relatively limited. As a result, we[5a], [5b], [5c], and others have synthesized interesting metallaheteroborane clusters containing selenium and tellurium that illustrate reactivity and structural patterns different from those containing sulfide …”

Section: Introductionmentioning

confidence: 99%

Chemistry of Triple‐Decker Sandwich Complexes Containing Four‐Membered Open B₂E₂ Rings (E = S or Se)

et al. 2018

Self Cite

View full text Add to dashboard Cite

Building upon our earlier studies of cobaltaheteroboranes, we explore the chemistry with heavier group 9 metals. Reaction of [Cp*M(μ-Cl)Cl x ] 2 (Cp* = η 5 -C 5 Me 5 ; M = Co, x = 0; M = Rh or Ir, x = 1) with [LiBH 4 ·THF], followed by thermolysis with an excess of chalcogen powders (S or Se), affords dimetallaheteroboranes nido-[(Cp*M) 2 B 2 H 2 E 2 ], 1-4 (1: E = S; 2: E = Se, M = Co; 3 and 4: E = Se, M = Rh and Ir, respectively) in moderate-to-good yields. The solid-state structures of these compounds show open-cage triple-decker clusters. Attempts to isolate the Te analogue have failed; however, in the case of cobalt, we have isolated an 11 skeletal-electron-pair nido-[(Cp*Co) 2 B 5 H 5 Te 2 ], 5. The X-ray diffraction structure of 5 shows monocapped square antiprismatic geometry, with two Te atoms in the core. To close the central four-membered B 2 E 2 open ring [a]

show abstract

Metallaheteroborane clusters of group 5 transition metals derived from dichalcogenide ligands

Cited by 26 publications

References 37 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

Metal–Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc

Chemistry of Triple‐Decker Sandwich Complexes Containing Four‐Membered Open B₂E₂ Rings (E = S or Se)

Contact Info

Product

Resources

About

Metallaheteroborane clusters of group 5 transition metals derived from dichalcogenide ligands

Cited by 26 publications

References 37 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

Metal–Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc

Chemistry of Triple‐Decker Sandwich Complexes Containing Four‐Membered Open B2E2 Rings (E = S or Se)

Contact Info

Product

Resources

About

Chemistry of Triple‐Decker Sandwich Complexes Containing Four‐Membered Open B₂E₂ Rings (E = S or Se)