Investigation of the dithiocarbamate-induced coupling of allylidene and carbonyl ligands on a tungsten center

Marianna F. Asaroa; Andreas Mayr; Bart Kahra; Donna Van Engen

doi:10.1016/0020-1693(94)03886-4

Investigation of the dithiocarbamate-induced coupling of allylidene and carbonyl ligands on a tungsten center

Marianna F. Asaroa
, Andreas Mayr
, Bart Kahra
, Donna Van Engen

Chemistry

Princeton University

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

Reaction of the allylidene tungsten complex [W(CPhCHCHMe)Br₂(CO)₂(4-picoline)] (1) with the dithiocarbamates MS₂CNR₂ (a: M=Na, R=Et; b: M=Na, R=Me; c: M=Li, R=Ph) in THF at 50 °C affords the vinylketene tungsten complexes [W(S₂CNR₂)₂(OCCPhCHCHMe)(CO)] (2a-c). At lower temperatures, four reaction intermediates (3-6) may be discerned. Spectroscopic studies indicate that these compounds contain η⁴-allyldithiocarbamate ligands which are generated by addition of dithiocarbamate across the metal-carbon double bond of the allylidene-tungsten unit in 1. The structures of [W(S₂CNEt₂)₂(OCCPhCHCHMe)(CO)] (2a) and of one intermediate, [W(η⁴-Et₂NCS₂CPhCHCHMe)(S₂CNEt₂)(CO)₂] (5a) were elucidated by X-ray crystallography.

Original language	English
Pages (from-to)	335-346
Number of pages	12
Journal	Inorganica Chimica Acta
Volume	220
Issue number	1-2
DOIs	https://doi.org/10.1016/0020-1693(94)03886-4
State	Published - Jun 1 1994

Keywords

Alkylidene complexes
Carbonyl complexes
Coupling reaction
Dithiocarbamate ligand
Tungsten complexes

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10.1016/0020-1693(94)03886-4

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@article{b6af352fcfad4a6788415c84baa5dc6a,

title = "Investigation of the dithiocarbamate-induced coupling of allylidene and carbonyl ligands on a tungsten center",

abstract = "Reaction of the allylidene tungsten complex [W(CPhCHCHMe)Br2(CO)2(4-picoline)] (1) with the dithiocarbamates MS2CNR2 (a: M=Na, R=Et; b: M=Na, R=Me; c: M=Li, R=Ph) in THF at 50 °C affords the vinylketene tungsten complexes [W(S2CNR2)2(OCCPhCHCHMe)(CO)] (2a-c). At lower temperatures, four reaction intermediates (3-6) may be discerned. Spectroscopic studies indicate that these compounds contain η4-allyldithiocarbamate ligands which are generated by addition of dithiocarbamate across the metal-carbon double bond of the allylidene-tungsten unit in 1. The structures of [W(S2CNEt2)2(OCCPhCHCHMe)(CO)] (2a) and of one intermediate, [W(η4-Et2NCS2CPhCHCHMe)(S2CNEt2)(CO)2] (5a) were elucidated by X-ray crystallography.",

keywords = "Alkylidene complexes, Carbonyl complexes, Coupling reaction, Dithiocarbamate ligand, Tungsten complexes",

author = "Asaroa, \{Marianna F.\} and Andreas Mayr and Bart Kahra and \{Van Engen\}, Donna",

year = "1994",

month = jun,

day = "1",

doi = "10.1016/0020-1693(94)03886-4",

language = "English",

volume = "220",

pages = "335--346",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

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TY - JOUR

T1 - Investigation of the dithiocarbamate-induced coupling of allylidene and carbonyl ligands on a tungsten center

AU - Asaroa, Marianna F.

AU - Mayr, Andreas

AU - Kahra, Bart

AU - Van Engen, Donna

PY - 1994/6/1

Y1 - 1994/6/1

N2 - Reaction of the allylidene tungsten complex [W(CPhCHCHMe)Br2(CO)2(4-picoline)] (1) with the dithiocarbamates MS2CNR2 (a: M=Na, R=Et; b: M=Na, R=Me; c: M=Li, R=Ph) in THF at 50 °C affords the vinylketene tungsten complexes [W(S2CNR2)2(OCCPhCHCHMe)(CO)] (2a-c). At lower temperatures, four reaction intermediates (3-6) may be discerned. Spectroscopic studies indicate that these compounds contain η4-allyldithiocarbamate ligands which are generated by addition of dithiocarbamate across the metal-carbon double bond of the allylidene-tungsten unit in 1. The structures of [W(S2CNEt2)2(OCCPhCHCHMe)(CO)] (2a) and of one intermediate, [W(η4-Et2NCS2CPhCHCHMe)(S2CNEt2)(CO)2] (5a) were elucidated by X-ray crystallography.

AB - Reaction of the allylidene tungsten complex [W(CPhCHCHMe)Br2(CO)2(4-picoline)] (1) with the dithiocarbamates MS2CNR2 (a: M=Na, R=Et; b: M=Na, R=Me; c: M=Li, R=Ph) in THF at 50 °C affords the vinylketene tungsten complexes [W(S2CNR2)2(OCCPhCHCHMe)(CO)] (2a-c). At lower temperatures, four reaction intermediates (3-6) may be discerned. Spectroscopic studies indicate that these compounds contain η4-allyldithiocarbamate ligands which are generated by addition of dithiocarbamate across the metal-carbon double bond of the allylidene-tungsten unit in 1. The structures of [W(S2CNEt2)2(OCCPhCHCHMe)(CO)] (2a) and of one intermediate, [W(η4-Et2NCS2CPhCHCHMe)(S2CNEt2)(CO)2] (5a) were elucidated by X-ray crystallography.

KW - Alkylidene complexes

KW - Carbonyl complexes

KW - Coupling reaction

KW - Dithiocarbamate ligand

KW - Tungsten complexes

UR - https://www.scopus.com/pages/publications/26544471169

U2 - 10.1016/0020-1693(94)03886-4

DO - 10.1016/0020-1693(94)03886-4

M3 - Article

AN - SCOPUS:26544471169

SN - 0020-1693

VL - 220

SP - 335

EP - 346

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

IS - 1-2

ER -

Investigation of the dithiocarbamate-induced coupling of allylidene and carbonyl ligands on a tungsten center

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Keywords

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