Die zweikernkomplexe (μ-S)[CpW(CO)3]2 und (μ-CH2S)[CpW(CO)2]2

Herberhold, Max; Jellen, W.; Murray, H. H.

doi:10.1016/0022-328x(84)80335-6

Cited by 24 publications

(8 citation statements)

References 17 publications

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“…1074 The reaction of [WH(CO) 3 Cp] with S(NMe 2 ) 2 produces [{W(CO) 3 Cp} 2 (u-S)], which reacts with CH 2 N 2 to give the thioformaldehyde complex [W 2 (CO) 4 (u-SCH 2 )Cp 2 ]. 1075 can also be isolated. 1076 ' 1077 A similar insertion reaction of R'N=S=O and R'N=S=NR 2 (R 1 = aryl, R 2 = SO 2 aryl) has been reported.…”

Section: Tungsten Complexes With Sulfur And/or Thiolate Ligandsmentioning

confidence: 96%

Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

Morris

1995

Comprehensive Organometallic Chemistry II

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Section: Tungsten Complexes With Sulfur And/or Thiolate Ligandsmentioning

confidence: 96%

Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

Morris

1995

Comprehensive Organometallic Chemistry II

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“…At room temperature complex 7 displays fluxionality on the allylic part of the molecule, namely the allylic ligand undergoes interconversion between endo and exo forms. Thus, in the 13 C NMR spectrum obtained at room temperature, sharp reson- In the presence of Fe(CO) 5 , allenes and aldehydes give substi- 75.9(6) 75.1(6) 109. 7(6) 82.1(5) 76.9(6) 134.…”

Section: Reaction Of Complex 2 With Allenementioning

confidence: 97%

“…It has been reported that the reaction of WCp(CO) 3 H with S(NMe 2 ) 2 affords the dinuclear S-bridging tungsten complex [WCp(CO) 3 ] 2 (µ-S) which, upon reacting with CH 2 N 2 , gives the thioformaldehyde complex [WCp(CO) 2 ] 2 (µ-CH 2 S). 13 Conversion of complex 2 into 3 involves substitution of the ketene oxygen with sulfur and a change of co-ordination mode. A possible mechanism for the formation of 3 is depicted in Scheme 1.…”

Section: Reactions Of Complex 2 With Isothiocyanatementioning

confidence: 99%

“…1 H NMR, (CDCl 3 ): δ 6.32 (d, J H-H = 0.88, J W-H = 6.90, 1 H, ᎐ ᎐ CH); 5.93 (d, J H-H = 0.88 Hz, 1 H, ᎐ ᎐ CH); 5.53, 5.42 (s, Cp). 13 C NMR, (CDCl 3 ): δ 242.…”

Section: Reaction Of Complex 2 With Phch 2 Ncs At Room Temperaturementioning

confidence: 99%

“…These resonances are downfield relative to those of the ketene ligand of 2 (δ 3.41) and are characteristic of olefinic ᎐ ᎐ CH 2 methylene protons. The two 13 C resonances of the thioketene ligand occur at δ 117.9 (terminal carbon) and 166.5, and show 1 J C-H and 2 J C-H coupling with the olefinic protons; assignments were made via two dimensional heteronuclear multiple quantum and multiple bond correlation (HMQC and HMBC) NMR techniques. 10 Scheme 1…”

Section: Reactions Of Complex 2 With Isothiocyanatementioning

confidence: 99%

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Reactions of a dinuclear tungsten complex containing an O-co-ordinated bridging ketene with various heterocumulenes

Wang¹,

You²,

Huang³

et al. 1999

J. Chem. Soc., Dalton Trans.

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Treatment of the dinuclear O-co-ordinated ketene complex W 2 Cp 2 (CO) 5 (µ-η 1 : η 2 -CH 2 CO) (Cp = η 5 -C 5 H 5 ) with PhCH 2 NCS afforded the dark red bridging thioketene complex W 2 Cp 2 (CO) 5 (µ-η 3 -SC᎐ ᎐ CH 2 ). Reaction of the latter with HBF 4 gave the stable cationic product [W 2 Cp 2 (CO) 5 (µ-SCMe 3 )]BF 4 by addition of a proton to the terminal carbon of the thioketene group. In the reaction of W 2 Cp 2 (CO) 5 (µ-η 1 : η 2 -CH 2 CO) with CS 2 cleavage of one CS bond is accompanied by insertion of the resulting sulfur atom into the tungsten-acyl bond to afford W 2 Cp 2 (CO) 5 (CS)-(µ-CH 2 COS). The CpЈ analogue (CpЈ = η 5 -C 5 H 4 Me) was also prepared. The reaction of the trithiocarbonate S᎐ ᎐ C(SCH 2 ) 2 with W 2 Cp 2 (CO) 5 (µ-η 1 : η 2 -CH 2 CO) afforded the carbene complex W 2 Cp 2 (CO) 5 [C(SCH 2 ) 2 ](µ-CH 2 COS), and with allene gave the allylic complex W 2 Cp 2 (CO) 5 (µ-η 1 : η 3 -CH 2 COC 3 H 4 ). Those of the complexes have been characterized by single crystal X-ray diffraction analysis.

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Cobaltkomplexe mit Thio‐ und Selenoaldehyden sowie mit den chelatbildenden Dianionen (CH₃)₂CS₂²⁻ und (CH₃)₂CSe₂²⁻ als Liganden

Hofmann

Werner

1985

Chem. Ber.

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Durch Reaktion von C5H5Co(CO)PMe3 und CsHSCo(CO)PMe2Ph mit CH2Xz (X = Br, I) und NaSH bzw. NaSeH werden die Thio-und Selenoformaldehyd-Cobaltkomplexe CSH5Co(q2-CHzE)PMe3 (E = S, Se; 1, 2) und CSH5Co(q2-CH2S)PMe2Ph (3) synthetisiert. Bei Verwendung von CH3CHBr2 an Stelle von CH2Brz entstehen die Verbindungen CSHsCo-(q2-CH3CHE)PMe3 (E = S, Se; 4, 5) als erste Vertreter von Thio-bzw. SelonoacetaldehydMetallkomplexen. Die Umsetzung von C5HSCo(CO)PMe3 rnit (CH3)2CBr2 und NaSH bzw.NaSeH ergibt die Verbindungen CSH5Co(E2C(CH3)z)PMe3 (E = S, Se; 6, 7), die einen The reactions of CSH5Co(CO)PMe3 and CSHSCo(CO)PMe2Ph with CHzX2 (X = Br, I) in the presence of NaSH or NaSeH led to the thio-and selenoformaldehyde cobalt complexes CSHSCo(q2-CH2E)PMe3 (E = S, Se; 1, 2) and CSH5Co(q2-CH2S)PMe2Ph (3), respectively. By using CH3CHBrz instead of CH2Br2, the compounds C5HSCo(q2-CH3CHE)PMe3 (E = S, Se; 4,. 5) are formed which represent the first metal complexes with thio-and selenoacetaldehyde as ligands. The reactions of C5HSCo(CO)PMe3 with (CH3)2CBr2 and NaSH or NaSeH lead to the compounds CSH5Co(E2C(CH3)2)PMe3 (E = S, Se; 6, 7) containing a four-membered CoE2C ring. Electrophiles such as HBF4 or CH31 react with Thio-und Selenocarbonyl-Verbindungen R2C = S und R2C = Se weisen gegenuber den homologen Carbonylderivaten R2C = 0 charakteristische Unterschiede auf, deren Ursachen in erster Linie in der weniger effektiven uberlappung der p(C)-p(E)-Orbitale im Fall von E = S und Se zu suchen sind'). Aufgrund der hohen Reaktivitat der C = S-bzw. C = Se-Doppelbindung sind Vertreter dieser Verbindungsklasse oft extrem reaktiv und daher in monomerer Form nur in der Gasphase nachweisbar').

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Die zweikernkomplexe (μ-S)[CpW(CO)3]2 und (μ-CH2S)[CpW(CO)2]2

Cited by 24 publications

References 17 publications

Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

Reactions of a dinuclear tungsten complex containing an O-co-ordinated bridging ketene with various heterocumulenes

Cobaltkomplexe mit Thio‐ und Selenoaldehyden sowie mit den chelatbildenden Dianionen (CH₃)₂CS₂²⁻ und (CH₃)₂CSe₂²⁻ als Liganden

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Die zweikernkomplexe (μ-S)[CpW(CO)3]2 und (μ-CH2S)[CpW(CO)2]2

Cited by 24 publications

References 17 publications

Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

Reactions of a dinuclear tungsten complex containing an O-co-ordinated bridging ketene with various heterocumulenes

Cobaltkomplexe mit Thio‐ und Selenoaldehyden sowie mit den chelatbildenden Dianionen (CH3)2CS22− und (CH3)2CSe22− als Liganden

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Cobaltkomplexe mit Thio‐ und Selenoaldehyden sowie mit den chelatbildenden Dianionen (CH₃)₂CS₂²⁻ und (CH₃)₂CSe₂²⁻ als Liganden