Transition metal boryl complexes: structure and reactivity of CpFe(CO)2Bcat and CpFe(CO)2BPh2

Hartwig, John F.; Huber, Susan

doi:10.1021/ja00064a069

Cited by 134 publications

(102 citation statements)

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“…The multinuclear NMR spectra of these mixtures, however, show no signifi-bility of 11a, b towards air and water is in sharp contrast to the known reactivity of [µ-BN(SiMe 3 ) 2 (µ-CO){(η 5 -pect a reduced, and probably more selective, reactivity with respect to salt eliminations. [16] Indeed, the reaction of C 5 with substitution of only one halide according to Equation similar stability. One might expect the electron-withdrawing effect of the nitrogen bound SiMe 3 groups and, hence, the 2.…”

Section: Iron Complexesmentioning

confidence: 99%

Boryl and Bridged Borylene Complexes of Iron and Ruthenium

Braunschweig¹,

Kollann

Klinkhammer

1999

Eur. J. Inorg. Chem.

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The reactivity of aminodihaloboranes R2NBX2 (R = Me, SiMe3; × = Cl, Br) towards transition metal complexes of the type Na[(η5‐C5R′5)M(CO)2)] (M = Fe, Ru; R′ = H, Me) was investigated. In the case of Me2NBBr2 and M = Fe the borylcomplexes [(η5‐C5R′5)(CO)2Fe{BBr(NMe2)}] (C5R′5 = C5H59a; C5R′5 = C5H4Me 9b; C5R′5 = C5Me510) were obtained. The compounds 9aand 9bwere formed together with the corresponding bridged borylene complexes [μ‐BNMe2(μ‐CO){(η5‐C5R′5)Fe(CO)}2] (C5R′5 = C5H511a; C5R′5 = C5H4Me 11b) in a 1:1 ratio, the latter, however, could be isolated from these mixtures as pure materials. In addition the novel boryl and borylene ruthenium complexes [(η5‐C5H5)(CO)2Ru{BX(NMe2)}] (X = Cl 12a; × = Br 12b), [(η5‐C5H5)(CO)2Ru{BCl{NSiMe3{BClN(SiMe3)2}}}] (13) and [μ‐BN(SiMe3)2(μ‐CO){(η5‐C5H5)Ru(CO)}2] (14) were obtained by similar methods. All compounds were characterized by multinuclear NMR and IR spectroscopy. The structure of 13 in the solid state was determined by a single‐crystal X‐ray diffraction study.

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Section: Iron Complexesmentioning

confidence: 99%

Boryl and Bridged Borylene Complexes of Iron and Ruthenium

Braunschweig¹,

Kollann

Klinkhammer

1999

Eur. J. Inorg. Chem.

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“…Examples of iron boryl complexes that react with H 2 to form iron hydrides and borane may proceed similarly. [91,92] . [43] Of course, such steps are closely related to those commonly observed at d 0 centers, such as the reactions leading to polysilane formation.…”

Section: Mh(ch 2 R) Via M(h 2 -H-ch 2 R)mentioning

confidence: 99%

The σ‐CAM Mechanism: σ Complexes as the Basis of σ‐Bond Metathesis at Late‐Transition‐Metal Centers

2007

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Complexes in which a sigma-H--E bond (E=H, B, Si, C) acts as a two-electron donor to the metal center are called sigma complexes. Clues that it is possible to interconvert sigma ligands without a change in oxidation state derive from C--H activation reactions effecting isotope exchange and from dynamic rearrangements of sigma complexes (see Frontispiece). Through these pathways, metathesis of M--E bonds can occur at late transition metals. We call this process sigma-complex-assisted metathesis, or sigma-CAM, which is distinct from the familiar sigma-bond metathesis (typical for d(0) metals and requiring no intermediate) and from oxidative-reductive elimination mechanisms (inherently requiring intermediates with changed oxidation states and sometimes involving sigma complexes). There are examples of sigma-CAM mechanisms in catalysis, especially for alkane borylation and isotope exchange of alkanes. It may also occur in silylation and alkene hydrogenation.

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“…13 C NMR: δ ϭ 13.7, 14.2 (CH 3 ), 18.5, 19.0 (CH 2 ), 103.4 (br., B-bound basal C atoms), 112.9 (skeletal C atoms non-adjacent to the basal B atom), 126. 8,127.2,128.8,133.2,141.3 (Ph) -1-iodo-6-(trimethylstannyl)-2,3,4,5-tetracarbanido-hexaborane(6) (7a): A solution of 1 (194 mg, 0.44 mmol) in hexane (10 mL) was added to a suspension of Me 3 SnLi (1 mmol) in hexane (20 mL) at Ϫ60°C.…”

Section: 345-tetraethyl-6-hydrido-1-iodo-2345-tetracarba-nido-mentioning

confidence: 99%

“…13 C NMR: δ ϭ Ϫ6.0 (SnMe 3 ), 13.5, 14.1 (CH 3 ), 19.2, 22.2 (CH 2 ), signals of B-bound basal C atoms not observed, 118.6 (skeletal C atoms non-adjacent to the basal B atom) ppm.…”

Section: 345-tetraethylmentioning

confidence: 99%

Reactivity Studies on 2,3,4,5‐Tetraethyl‐1,6‐diiodo‐2,3,4,5‐tetracarba‐nido‐hexaborane(6): Synthesis and Structures of New C₄B₂nido‐Carborane Derivatives

2004

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Keywords: Boron / Carboranes / Nucleophilic substitution / Iron / CobaltThe reactivity of the title compound 2,3,4,5-tetraethyl-1,6-diiodo-2,3,4,5-tetracarba-nido-hexaborane(6) (1) towards a variety of nucleophiles is reported. When 1 is treated with RC 2 Li (R = Ph, tBu, SiMe 3 , p-tolyl) and Ph 2 PLi, the corresponding new C 4 B 2 nido-carborane derivatives 2a−d and 3, respectively, are obtained by selective substitution at the basal B−I group, whereas the apical B−I bond remains inert. The reaction of 1 with K[(η 5 -C 5 H 5 )Fe(CO) 2 ] affords the novel species 4, which contains a CpFe(CO) 2 fragment σ-bonded to the basal boron atom of the C 4 B 2 cluster. Attempts to isolate 4 by chromatography on silica gel led to cleavage of the Fe−B bond and formation of compound 5, containing a basal BH vertex, which can be separately prepared by the reaction of 1 and LiBEt 3 H. In the reactions of 1 with PhLi and Me 3 SnLi, respectively, 6a and 7a are formed as the predominant B6-substituted carborane products. In addition, trace amounts of

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Transition metal boryl complexes: structure and reactivity of CpFe(CO)2Bcat and CpFe(CO)2BPh2

Cited by 134 publications

References 0 publications

Boryl and Bridged Borylene Complexes of Iron and Ruthenium

Boryl and Bridged Borylene Complexes of Iron and Ruthenium

The σ‐CAM Mechanism: σ Complexes as the Basis of σ‐Bond Metathesis at Late‐Transition‐Metal Centers

Reactivity Studies on 2,3,4,5‐Tetraethyl‐1,6‐diiodo‐2,3,4,5‐tetracarba‐nido‐hexaborane(6): Synthesis and Structures of New C₄B₂nido‐Carborane Derivatives

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Transition metal boryl complexes: structure and reactivity of CpFe(CO)2Bcat and CpFe(CO)2BPh2

Cited by 134 publications

References 0 publications

Boryl and Bridged Borylene Complexes of Iron and Ruthenium

Boryl and Bridged Borylene Complexes of Iron and Ruthenium

The σ‐CAM Mechanism: σ Complexes as the Basis of σ‐Bond Metathesis at Late‐Transition‐Metal Centers

Reactivity Studies on 2,3,4,5‐Tetraethyl‐1,6‐diiodo‐2,3,4,5‐tetracarba‐nido‐hexaborane(6): Synthesis and Structures of New C4B2nido‐Carborane Derivatives

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Reactivity Studies on 2,3,4,5‐Tetraethyl‐1,6‐diiodo‐2,3,4,5‐tetracarba‐nido‐hexaborane(6): Synthesis and Structures of New C₄B₂nido‐Carborane Derivatives