Nackte hauptgruppenelemente als trigonal planar gebundene μ3-brückenliganden

Hüttner, Gottfried; Weber, Ute; Sigwarth, Beate; Scheidsteger, Olaf; Lang, Heinrich; Zsolnai, László

doi:10.1016/0022-328x(85)87192-8

Cited by 107 publications

(56 citation statements)

References 28 publications

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“…If L M has7t-orbitals of different donor quality (e.g. Cp(CO)2Mn) the better fl-donor orbita will be vertical to the MXM plane (11,19,22,38). All compounds (LnM)2XR show bright colours, which is easily understood in terms of allowed electronic transitions (10) in the 3-center-4-system (Scheme 2).…”

Section: Lmx(r)hal2mentioning

confidence: 99%

“…Substitution by organometallic nucleophiles leads to compounds containing "naked" trigonally planar coordinated X atoms (see below) (37,38).…”

Section: Lmx(r)hal2mentioning

confidence: 99%

“…Compounds containing triply bridging X atoms in a planar coordination may be described as organometallic substitution products of "-inidene" complexes. In fact many of these species (37,38,43) including the first examples of this type of coordination (37) have been synthesized from "-inidene" compounds as the starting materials. One example has already been given above and Scheme 3 illustrates a selection of structurally fully characterized compounds.…”

Section: Lmx(r)hal2mentioning

confidence: 99%

“…Mn(C0Cp Two reactions may serve to illustrate the synthetic principles: ((CO)5W)2SbC1 reacts with Na2W2(CO)10 to give the symmetric anion Sb(W(CO)5)3 (38).…”

Section: Cr(c0)mentioning

confidence: 99%

“…(C0)5WW(C0)5 (C0)5WW(C0)5 (38) Treatment of ((CO)5Cr)2AsCl with Mn(CO)5 yields the substitution product first, which then decarbonylates to the more condensed species, which again contains a planar p3_arsenic…”

Section: Cr(c0)mentioning

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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Section: Lmx(r)hal2mentioning

confidence: 99%

“…Substitution by organometallic nucleophiles leads to compounds containing "naked" trigonally planar coordinated X atoms (see below) (37,38).…”

Section: Lmx(r)hal2mentioning

confidence: 99%

Section: Lmx(r)hal2mentioning

confidence: 99%

“…Mn(C0Cp Two reactions may serve to illustrate the synthetic principles: ((CO)5W)2SbC1 reacts with Na2W2(CO)10 to give the symmetric anion Sb(W(CO)5)3 (38).…”

Section: Cr(c0)mentioning

confidence: 99%

Section: Cr(c0)mentioning

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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The 1,3-Sn2O2-Heterocycle as a Ligand in Organometallic Compounds – Dimerization of the Inidene Species [{(CO)5M}2SnOR]– (M = Cr, W)

Kircher

Hüttner²,

Heinze

et al. 1998

Eur. J. Inorg. Chem.

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Dimerized inidene complexes [(CO)5M−Sn(OR)−M(CO)5]22– (M = Cr, W; R = Et, iPr), 1, are obtained from [{(CO)5M}2SnCl2]2– by different routes. Dimerization occurs via alkoxy‐donor tin‐acceptor bonding by which a planar Sn2O2 ring is formed. The Sn–{M(CO)5} bonds are made in a plane vertical to this ring such that, with the R–O groups being almost coplanar with the Sn2O2 ring, the overall geometry of the compounds shows idealized D2h symmetry. – The 119Sn‐NMR resonances of 1 are found at rather low fields (M = Cr: δ ≈ 1400; M = W: δ ≈ 1170) indicating a low‐lying tin‐centered orbital in the LUMO range. Correspondingly EHT analyses show that the 3‐center‐4π system, which characterizes monomeric inidene species [LnM−E(X)−MLn]n, is still prevalent in the dimeric species 1. The low‐lying π*‐type LUMOs of 1 are the rationale for the observed 119Sn‐NMR low‐field shifts of 1. The dimeric compounds 1 react with 2,4‐pentanedione to form chelate compounds of the same type as those characteristically obtained from monomeric inidene complexes: [{(CO)5Cr}2SnOEt]22– (1a) reacts to give [{(CO)5Cr}2Sn(acac)]– (2). The experimental results are verified by X‐ray analyses in addition to the usual spectroscopic and analytical investigations.

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Synthesis of the Germanium(I) Compounds [Ge2Hal4]2– and Their Reductive Condensation to Octahedral [Ge6]2– Clusters in an Organometallic Environment

Renner

Kircher

Hüttner

et al. 2000

Eur. J. Inorg. Chem.

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GeI2 reacts with [M2(CO)10]2– (M = Cr, W) leading to reductive coupling of two GeI2 units to produce the [Ge2I4]2– ligands of [{(OC)5M}I2Ge–GeI2{M(CO)5}]2– (1a and 2a). The [Ph4P] salts of these anions have been characterised by X‐ray structure analyses as have the [Ph4P] salts of [{(OC)5M}Cl2Ge–GeCl2{M(CO)5}]2– (1b and 2b) obtained from the iodo derivatives 1a and 2a by halide metathesis with [Ph4P]Cl. Treatment of GeI2 with [W2(CO)10]2– in the presence of 2,2′‐bipyridine leads to [{(OC)5W}I2Ge–Ge(bipy){W(CO)5}] (3). The digermanium ligands in 1–3 contain germanium in the unconventional formal oxidation state +I. Reductive condensation of [{(OC)5Cr}I2Ge–GeI2{Cr(CO)5}]2– (1a) by addition of [Cr2(CO)10]2– leads to the octahedral cluster [{(OC)5Cr}6Ge6]2– (4) in a yield of 40%. The sequence of reactions as reported describes the first systematic approach to the synthesis of [E6]2– clusters.

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Nackte hauptgruppenelemente als trigonal planar gebundene μ3-brückenliganden

Cited by 107 publications

References 28 publications

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

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

The 1,3-Sn2O2-Heterocycle as a Ligand in Organometallic Compounds – Dimerization of the Inidene Species [{(CO)5M}2SnOR]– (M = Cr, W)

Synthesis of the Germanium(I) Compounds [Ge2Hal4]2– and Their Reductive Condensation to Octahedral [Ge6]2– Clusters in an Organometallic Environment

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