Valenztautomerie an stibiniden-komplexen. Synthese von stiban und distiben-komplexen

Weber, Ute; Hüttner, Gottfried; Scheidsteger, Olaf; Zsolnai, László

doi:10.1016/0022-328x(85)87412-x

Cited by 49 publications

(17 citation statements)

References 18 publications

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“…This is consistent with the fact that n bonded complexes of the q2 type have always been observed for distibenes. [6][7][8][9] 11 The dimerizations of 3 and 4, giving cyclic (SbH)4 and (BiH)4 compounds, were 38.0 and 35.9 kcal mol-1 (exothermic) while those of 1 and 2 were 28.9 and 37.5 kcal mol-1 (exothermic) at the MP4/DZ( d ,p)//HF/DZ( d ,p) level, respectively.…”

mentioning

confidence: 99%

Do distibene (HSbSbH) and dibismuthene (HBiBiH) feature double bonding? A theoretical comparison with diphosphene (HPPH) and diarsene (HAsAsH)

Nagase¹,

Suzuki²,

Kurakake³

1990

J. Chem. Soc., Chem. Commun.

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Ab initio calculations suggest that the Sb and Bi atoms in group 15 form double bonded compounds, as do the lighter P and As atoms, unlike the heavier Sn and Pb in group 14; dibismuthenes are the heaviest example of double bonding between main group elements.Compounds featuring double bonding between the heavier group 15 elements are of current interest.1 In 1981, the first stable P-P double bonded compound, a diphosphene derivative (RP=PR), was synthesized and isolated.2 Since then, many schemes have been revised and diphosphenes are now commonplace. 1 In addition, compounds with an -As=Aslinkage, diarsenes, have also been successfully synthesized and is0lated.3-~ However, attempts to prepare the heavier analogues, distibenes (RSb=SbR) and dibismuthenes (RBi= BiR), have all been unsuccessful up to now, except for the metal-coordinated distibene complexes, but these lose double bond character because of side-on q2 coordination."9The lighter Si and Ge atoms in group 14 can form isolable ethene analogues ,lo disilenes (R2Si=SiR2)11 and digermenes (R2Ge=GeR2).I2 However, the heavier Sn is reluctant to form double bonds in distannenes ( R2Sn=SnR2) ,13,14 while Pb does not form a diplumbene (R2Pb=PbR2) structure at a11.15-1h From this point of view, it is important to determine if the heavier atoms in group 15 are also incapable of forming double bonded compounds. For this purpose, we have undertaken the first ab initio calculations of the parent compounds, HSb=SbH 3 and HBi=BiH 4.Geometries were fully optimized at the Hartree-Fock (HF) level with relativistic effective core potentials (ECP)17 on Sb and Bi using the double-zeta (DZ) basis sets17 augmented by a set of d-type polarization functions [d exponents18 0.211 (Sb) and 0.185 (Bi)]. The D Z basis set19 for H was scaled by a factor

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confidence: 99%

Do distibene (HSbSbH) and dibismuthene (HBiBiH) feature double bonding? A theoretical comparison with diphosphene (HPPH) and diarsene (HAsAsH)

Nagase¹,

Suzuki²,

Kurakake³

1990

J. Chem. Soc., Chem. Commun.

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“…Both forms were isolated and characterized spectroscopically, though it was proposed that the open form could gradually convert into the closed form. [13b], It was also reported that the W 2 (CO) 10 (µ‐Sb t Bu) species, a reaction intermediate that was not isolated but characterized through its adducts with PPh 3 and W(CO) 5 , interconverted between a closed form with a W–W bond (type B2 ) and an open form without a W–W bond (type B1 ); the antimony atoms in these two forms are Lewis basic and acidic, respectively …”

Section: Resultsmentioning

confidence: 99%

Expedient Synthesis of a Metallostibine Os₂(CO)₈(µ‐SbPh): An Unusual and Strong Two‐Electron‐Donor Ligand

Ganguly

Leong

2017

Eur J Inorg Chem

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A metallostibine, Os2(CO)8(µ‐SbPh) (2), was generated readily and in high yield and purity from the Os3(CO)11(µ‐SbPh)(Cl)2 (1) cluster through elimination of the terminal Os(CO)3(Cl)2 Lewis acid fragment with activated γ‐alumina. Compound 2 is air sensitive in solution but relatively stable as a solid. The Sb atom in 2 adopts a trigonal pyramidal geometry in both the solid and solution states, with an active lone pair of electrons. Experimental and computational studies show that 2 is a strong two‐electron donor with a donor strength comparable to that of alkylphosphines.

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“…This 3-center-4'it'-model (4 electrons from the two metal atom lone pairs, no electron from the empty X-p valence orbital) is consistent with the properties of (LM)2XR compounds: It explains 1. the trigonally planar coordination of X 2. the short X---M bonds 3. the y_VIS spectra 4. the P-NMR shifts of (LM)2PR Structure, Spectra. The trigonally planar coordination with short M--X bond lengths is common to all (LM)2XR compounds (2)(3)(4)(5)(7)(8)(9)(10)(11)(12)(18)(19)(20)22). If L M has7t-orbitals of different donor quality (e.g.…”

Section: Lmx(r)hal2mentioning

confidence: 99%

“…BR LMML BI LM' ML 131 = Lewis-Base (13,15,17,20,36) The electron deficiency of the sextet species R-X is only partially removed by the interaction with filled metal orbitals in (LM)9XR. Thus, in accord with the above MO-scheme (Scheme 2) Lewis bases add to X to yield tetrahedrally coordinated X in the adducts (3-6, 13-17,20,22,36).…”

Section: Lmx(r)hal2mentioning

confidence: 99%

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Unconventional multiple bonds: coordination compounds of unstable Vth main group ligands

Hüttner¹

1986

Pure and Applied Chemistry

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-Phosphinidene-, arsinidene-and stibinidene-complexes LnMX(R)__ MLn (X = P, As, Sb) contain the main group center X in a tngonally planar environment. The properties of these species are dominated by strong backbonding from filled metal orbitals at the 16 electron groups LnM into the vacant p orbital of the sextett species R-X. The synthesis and properties of LnMX(R)MLn species as well as their chemical interrelation to compounds containing R-X=X-R or IXEXI ligands will be reported.

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Valenztautomerie an stibiniden-komplexen. Synthese von stiban und distiben-komplexen

Cited by 49 publications

References 18 publications

Do distibene (HSbSbH) and dibismuthene (HBiBiH) feature double bonding? A theoretical comparison with diphosphene (HPPH) and diarsene (HAsAsH)

Do distibene (HSbSbH) and dibismuthene (HBiBiH) feature double bonding? A theoretical comparison with diphosphene (HPPH) and diarsene (HAsAsH)

Expedient Synthesis of a Metallostibine Os₂(CO)₈(µ‐SbPh): An Unusual and Strong Two‐Electron‐Donor Ligand

Unconventional multiple bonds: coordination compounds of unstable Vth main group ligands

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Valenztautomerie an stibiniden-komplexen. Synthese von stiban und distiben-komplexen

Cited by 49 publications

References 18 publications

Do distibene (HSbSbH) and dibismuthene (HBiBiH) feature double bonding? A theoretical comparison with diphosphene (HPPH) and diarsene (HAsAsH)

Do distibene (HSbSbH) and dibismuthene (HBiBiH) feature double bonding? A theoretical comparison with diphosphene (HPPH) and diarsene (HAsAsH)

Expedient Synthesis of a Metallostibine Os2(CO)8(µ‐SbPh): An Unusual and Strong Two‐Electron‐Donor Ligand

Unconventional multiple bonds: coordination compounds of unstable Vth main group ligands

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Expedient Synthesis of a Metallostibine Os₂(CO)₈(µ‐SbPh): An Unusual and Strong Two‐Electron‐Donor Ligand