Half-Sandwich Group 8 Borylene Complexes: Synthetic and Structural Studies and Oxygen Atom Abstraction Chemistry

Pierce, Glesni A.; Vidović, Dragoslav; Kays, Deborah L.; Coombs, Natalie D.; Thompson, Amber L.; Jemmis, Eluvathingal D.; De, Susmita; Aldridge, Simon

doi:10.1021/om801215b

Cited by 56 publications

(58 citation statements)

References 96 publications

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“…The average MoeFe distance of 2.8385 Å is consistent with the presence of a single bond and markedly shorter than [(Cp*Mo) 2 B 5 H 9 Fe(CO) 3 ] [44]. The B1eMo2 distance of 2.077(5) Å lies in the range of those reported for the transition metal borylene complexes [45]. In 7, one of the molybdenum atoms (Mo1) covalently bonded to carbonyl group (C27eO7), which displaced out of the Fe1-Fe2-Mo1 triangular plane in the direction away from the Fe(CO) 3 groups.…”

Section: Isolation and Structural Characterization Of 6 Andsupporting

confidence: 77%

Synthesis and characterization of novel eleven-vertex dimetallaheteroborane clusters containing Heavier group 16 elements

Ponniah

Bharathan

Bose

et al. 2012

Journal of Organometallic Chemistry

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Section: Isolation and Structural Characterization Of 6 Andsupporting

confidence: 77%

Synthesis and characterization of novel eleven-vertex dimetallaheteroborane clusters containing Heavier group 16 elements

Ponniah

Bharathan

Bose

et al. 2012

Journal of Organometallic Chemistry

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“…[15] The CAAC Me unit, although nearly coplanar with its attached boron atom (torsion angle N-C5-B2-C1 171.88 8), forms aB ÀC bond (B2ÀC5 1.540 (5) ) that is somewhat longer than B-CAAC bonds observed recently wherein multiple bonding was inferred, for example,[B 2 (CAAC Me ) 2 ](1.459(2), 1.458(2) ) [16] ), both prepared by Aldridge and co-workers. [18] As mentioned above, the 11 BNMR signals of 2 were observed at d 26 and 37 ppm, the latter presumably corresponding to the alkylideneborane boron center, given its resemblance to the 11 BNMR signals of previously reported alkylideneborates (d 35, 40 ppm). [15] The 1 HNMR shift of the duryl para hydrogen nucleus of 2 (d 4.70 ppm) is shifted greatly to high field compared to that of the precursor 1 (d 7.00 ppm), [8] reflective of its h 6 -coordination in the latter complex.…”

Section: In Memory Of Heinrich Nçthmentioning

confidence: 52%

Mild and Complete Carbonyl Ligand Scission on a Mononuclear Transition Metal Complex

et al. 2016

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The complete scission of the carbon-oxygen bond of carbon monoxide, while frequently observed on bulk metals and with bimetallic and cluster transition metal complexes, is unknown with monometallic systems. Reaction of a zerovalent iron bis(borylene) complex with a cyclic (alkyl)(amino)carbene revealed a highly selective intramolecular cleavage of the C-O bond of a carbonyl ligand at room temperature, leading to the formation of a highly unusual iron complex containing a base-stabilized (bora)alkylideneborane ligand. DFT investigation of the reaction mechanism suggested that the two Lewis acidic borylene boron atoms cooperate to cleave the C-O multiple bond.

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“…[22] Likewise, the Mn À B distance (1.825(2) ) was shorter by more than 0.2 than those commonly found in manganese-boryl compounds (see above) and it was similar to that of the borylene species (9) ). [23] The two halfsandwich fragments were twisted by 59.48 with respect to each other.…”

Section: Synthesis Of Metalloborylene Complexesmentioning

confidence: 63%

Monohaloboryls (BHX⁻) as Bridging Ligands: Observable Dinuclear σ‐(Halo)boranyl Intermediates in the Synthesis of Metalloborylenes

Bauer

Braunschweig

Dewhurst

et al. 2012

Chemistry A European J

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Upon treating transition-metal-dihaloboryl complexes of the form [L(n)MBX(2)] with K[(η(5)-C(5)H(5))MnH(CO)(2)], salt elimination occurs along with a migration of the Mn-bound hydride ligand onto the boron atom, thereby forming dinuclear σ-(halo)boranyl complexes of the form [L(n)M(μ-BHX)Mn(CO)(2)(η(5)-C(5)H(5))]. Most of these complexes react further at room temperature to lose HX and provide metalloborylene complexes [L(n)M-B = Mn(CO)(2)(η(5)-C(5)H(5))]; however, when ML(n) = Re(CO)(5) the σ-(halo)boranyl complex decomposes into unidentifiable products. We found through DFT calculations that two electronically and structurally distinct forms of the intermediate σ-(halo)boranyl complexes exist, one of which easily loses HX and one that does not.

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Half-Sandwich Group 8 Borylene Complexes: Synthetic and Structural Studies and Oxygen Atom Abstraction Chemistry

Cited by 56 publications

References 96 publications

Synthesis and characterization of novel eleven-vertex dimetallaheteroborane clusters containing Heavier group 16 elements

Synthesis and characterization of novel eleven-vertex dimetallaheteroborane clusters containing Heavier group 16 elements

Mild and Complete Carbonyl Ligand Scission on a Mononuclear Transition Metal Complex

Monohaloboryls (BHX⁻) as Bridging Ligands: Observable Dinuclear σ‐(Halo)boranyl Intermediates in the Synthesis of Metalloborylenes

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Half-Sandwich Group 8 Borylene Complexes: Synthetic and Structural Studies and Oxygen Atom Abstraction Chemistry

Cited by 56 publications

References 96 publications

Synthesis and characterization of novel eleven-vertex dimetallaheteroborane clusters containing Heavier group 16 elements

Synthesis and characterization of novel eleven-vertex dimetallaheteroborane clusters containing Heavier group 16 elements

Mild and Complete Carbonyl Ligand Scission on a Mononuclear Transition Metal Complex

Monohaloboryls (BHX−) as Bridging Ligands: Observable Dinuclear σ‐(Halo)boranyl Intermediates in the Synthesis of Metalloborylenes

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Product

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Monohaloboryls (BHX⁻) as Bridging Ligands: Observable Dinuclear σ‐(Halo)boranyl Intermediates in the Synthesis of Metalloborylenes