Syntheses, crystal structures and DFT studies of [Me3EM(CO)5] (E=Sb, Bi; M=Cr, W), cis-[(Me3Sb)2Mo(CO)4], and [tBu3BiFe(CO)4]

Breunig, H. J.; Borrmann, Tobias; Lork, Enno; Moldovan, Ovidiu; Raţ, Ciprian I.; Wagner, R.P.

doi:10.1016/j.jorganchem.2008.11.022

Cited by 38 publications

(29 citation statements)

References 44 publications

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“…Second, these complexes can easily be expanded in the vertical dimension by switching from phosphorus to arsenic donor atoms, 9 and very likely to antimony and bismuth donor atoms. The iron bismuth bond length in Fe(CO) 4 (Bit-Bu 3 ) is 2.6269(9) Å, 35 as compared to a range of 2.2310(3) to 2.2705(8) Å for the iron phosphorus bonds in Table 3. This 14-18% increase should greatly attenuate the types of steric interactions analyzed in Fig.…”

Section: Towards Molecular Gyroscopesmentioning

confidence: 83%

Synthesis, reactivity, structures, and dynamic properties of gyroscope like iron complexes with dibridgehead diphosphine cages: pre- vs. post-metathesis substitutions as routes to adducts with neutral dipolar Fe(CO)(NO)(X) rotors

et al. 2016

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Three routes are explored to the title halide/cyanide complexes trans-Fe(CO)(NO)(X)(P((CH))P) (9c-X; X = Cl/Br/I/CN), the Fe(CO)(NO)(X) moieties of which can rotate within the diphosphine cages (ΔH/ΔS (kcal mol/eu) 5.9/-20.4 and 7.4/-23.9 for 9c-Cl and 9c-I from variable temperature C NMR spectra). First, reactions of the known cationic complex trans-[Fe(CO)(NO)(P((CH))P)] BF and BuN X give 9c-Cl/-Br/-I/-CN (75-83%). Second, reactions of the acyclic complexes trans-Fe(CO)(NO)(X)(P((CH)CH[double bond, length as m-dash]CH)) and Grubbs' catalyst afford the tris(cycloalkenes) trans-Fe(CO)(NO)(X)(P((CH)CH[double bond, length as m-dash]CH(CH))P) (m/X = 6/Cl,Br,I,CN, 7/Cl,Br, 8/Cl,Br) as mixtures of Z/E isomers (24-41%). Third, similar reactions of trans-[Fe(CO)(NO)(P((CH)CH[double bond, length as m-dash]CH))] BF and Grubbs' catalyst afford crude trans-[Fe(CO)(NO)P((CH)CH[double bond, length as m-dash]CH(CH))P)] BF (m = 6, 8). However, the C[double bond, length as m-dash]C hydrogenations required to consummate routes 2 and 3 are problematic. Crystal structures of 9c-Cl/-Br/-CN are determined. Although the CO/NO/X ligands are disordered, the void space within the diphosphine cages is analyzed in terms of horizontal and vertical constraints upon Fe(CO)(NO)(X) rotation and the NMR data. The molecules pack in identical motifs with parallel P-Fe-P axes, and without intermolecular impediments to rotation in the solid state.

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Section: Towards Molecular Gyroscopesmentioning

confidence: 83%

Synthesis, reactivity, structures, and dynamic properties of gyroscope like iron complexes with dibridgehead diphosphine cages: pre- vs. post-metathesis substitutions as routes to adducts with neutral dipolar Fe(CO)(NO)(X) rotors

et al. 2016

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“…The coordination chemistry of triorganobismuthines BiR 3 (Lewis base), mostly involves substituted metal carbonyl complexes [3,4,28], but no metal complexes with BiR 2 X or BiRX 2 ligands are known. The reactions of [M(CO) 5 (thf)] (M ¼ Cr or W) [29] with BiMe 2 Br in thf solution, followed by removal of the thf, extraction with n-hexane and subsequent removal of the n-hexane in vacuo, gave yellow solids which were identified by a combination of IR, 1 H and 13 C{ 1 H} NMR spectroscopies as mixtures of M(CO) 6 …”

Section: Reactions Of Bime 2 Br With Transition Metal Carbonyl Reagentsmentioning

confidence: 99%

“…and the known[28] [M(CO)5 (BiMe 3 )] complexes. The yields of the [M(CO) 5 (BiMe 3 )] are rather variable, but typically 25e30%.…”

mentioning

confidence: 99%

Lewis base complexes of methyldihalobismuthines BiMeX2 (X = Cl or Br)

Benjamin

Levason

Reid

et al. 2012

Journal of Organometallic Chemistry

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a b s t r a c tMethyldihalobismuthines, BiMeX 2 (X ¼ Cl or Br) prepared from MeLi and a stoichiometric amount of BiX 3 in thf, react with 1,10-phenanthroline, 2,2 0 -bipyridyl or Me 2 NCH 2 CH 2 NMe 2 (LÀL) in thf or MeCN to give [BiMeX 2 (LÀL)], which are poorly soluble in non-polar solvents. X-Ray structures of [BiMeBr 2 (LÀL)] and of [BiMeCl 2 (Me 2 NCH 2 CH 2 NMe 2 )] show discrete square pyramidal molecules with apical methyl groups, and no intermolecular contacts within the sum of the appropriate Van der Waals radii. The structure of BiMe 2 Br is a 1-D polymer chain with bromine bridges containing a pseudo-trigonal bipyramidal geometry at bismuth. The reactions of BiMe 2 X with the bidentate N-donor ligands result in disproportionation to also form [BiMeX 2 (LeL)]. An unusual [BiMeBr 4 ] 2À anion in the salt [Li(H 2 O)(1,10-phen) 2 ][Li(1,10-phen) 2 (m-Br)BiMeBr 3 ]$thf, was isolated as a by-product and shows a LiÀBrÀBi bridge to one of the Li cations. BiMe 2 Br disproportionates on reaction with [M(CO) 5 (thf)] (M ¼ Cr or W) to form [M(CO) 5 (BiMe 3 )].

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“…The same group went on to publish the structures of [(CO) 5 MBiMe 3 ] (M = Cr, W) alongside the stibine analogues [122]. A theoretical investigation of the bonding in such compounds indicated similar ligand properties between the stibines and corresponding bismuthines, with only a slight reduction of donor strength for the latter.…”

Section: ][Bf 4 ] By Reaction Of [Fp(thf)][bf 4 ] With P-ph 2 Bic 6 Hmentioning

confidence: 99%

Synthesis, structure and reactivity of complexes containing a transition metal–bismuth bond

Braunschweig

Cogswell

Schwab

2011

Coordination Chemistry Reviews

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Syntheses, crystal structures and DFT studies of [Me3EM(CO)5] (E=Sb, Bi; M=Cr, W), cis-[(Me3Sb)2Mo(CO)4], and [tBu3BiFe(CO)4]

Cited by 38 publications

References 44 publications

Synthesis, reactivity, structures, and dynamic properties of gyroscope like iron complexes with dibridgehead diphosphine cages: pre- vs. post-metathesis substitutions as routes to adducts with neutral dipolar Fe(CO)(NO)(X) rotors

Synthesis, reactivity, structures, and dynamic properties of gyroscope like iron complexes with dibridgehead diphosphine cages: pre- vs. post-metathesis substitutions as routes to adducts with neutral dipolar Fe(CO)(NO)(X) rotors

Lewis base complexes of methyldihalobismuthines BiMeX2 (X = Cl or Br)

Synthesis, structure and reactivity of complexes containing a transition metal–bismuth bond

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