Formal coupling of two alkylidyne ligands on a metal center

Andreas Mayr; Cecilia M. Bastos; Nancy Daubenspeck; Gregory A. McDermott

doi:10.1002/cber.19921250712

Formal coupling of two alkylidyne ligands on a metal center

Andreas Mayr
, Cecilia M. Bastos
, Nancy Daubenspeck
, Gregory A. McDermott

Chemistry

Stony Brook University
Princeton University

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

23 Scopus citations

Abstract

Reaction of the alkylidyne complexes [W(CR)Br(CO)₃L] [2b (L = CO; R = C₆H₄‐OMe‐4), 2c (L = CO, R = C₆H₄‐NMe₂‐4), 3a (L = PPh₃; R = Ph), and 3c (L = PPh₃; R = C₆H₄‐NMe₂‐4)] with methyllithium in THF at ‐78°C affords the alkylidyne acyl tungsten complexes Li[W(CR)(COMe)Br(CO)₃L] [4b (L = CO; R = C₆H₄‐OMe‐4), 4c (L = CO, R = C₆H₄‐NMe₂‐4), 5a (L = PPh₃; R = Ph), and 5c (L = PPh₃; R = C₆H₄‐NMe₂‐4)]. Reaction of complexes 4 and 5 with C₂O₂Br₂ at ‐78°C‐0°C in CH₂Cl₂ followed by addition of PPh₃ gives the alkyne complexes [WBr₂(CO)(CH₃C = CR)(PPh₃)₂] (6). The formation of the alkyne ligands in complexes 6 may be considered as the result of formal coupling of two alkylidyne ligands.

Original language	English
Pages (from-to)	1583-1588
Number of pages	6
Journal	Chemische Berichte
Volume	125
Issue number	7
DOIs	https://doi.org/10.1002/cber.19921250712
State	Published - Jul 1992

Keywords

Alkylidyne ligands
Carbon–carbon coupling
Tungsten complexes

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@article{b2c0b7f221b84a6696e804d39e208be6,

title = "Formal coupling of two alkylidyne ligands on a metal center",

abstract = "Reaction of the alkylidyne complexes [W(CR)Br(CO)3L] [2b (L = CO; R = C6H4‐OMe‐4), 2c (L = CO, R = C6H4‐NMe2‐4), 3a (L = PPh3; R = Ph), and 3c (L = PPh3; R = C6H4‐NMe2‐4)] with methyllithium in THF at ‐78°C affords the alkylidyne acyl tungsten complexes Li[W(CR)(COMe)Br(CO)3L] [4b (L = CO; R = C6H4‐OMe‐4), 4c (L = CO, R = C6H4‐NMe2‐4), 5a (L = PPh3; R = Ph), and 5c (L = PPh3; R = C6H4‐NMe2‐4)]. Reaction of complexes 4 and 5 with C2O2Br2 at ‐78°C‐0°C in CH2Cl2 followed by addition of PPh3 gives the alkyne complexes [WBr2(CO)(CH3C = CR)(PPh3)2] (6). The formation of the alkyne ligands in complexes 6 may be considered as the result of formal coupling of two alkylidyne ligands.",

keywords = "Alkylidyne ligands, Carbon–carbon coupling, Tungsten complexes",

author = "Andreas Mayr and Bastos, \{Cecilia M.\} and Nancy Daubenspeck and McDermott, \{Gregory A.\}",

year = "1992",

month = jul,

doi = "10.1002/cber.19921250712",

language = "English",

volume = "125",

pages = "1583--1588",

journal = "Chemische Berichte",

issn = "0009-2940",

number = "7",

}

TY - JOUR

T1 - Formal coupling of two alkylidyne ligands on a metal center

AU - Mayr, Andreas

AU - Bastos, Cecilia M.

AU - Daubenspeck, Nancy

AU - McDermott, Gregory A.

PY - 1992/7

Y1 - 1992/7

N2 - Reaction of the alkylidyne complexes [W(CR)Br(CO)3L] [2b (L = CO; R = C6H4‐OMe‐4), 2c (L = CO, R = C6H4‐NMe2‐4), 3a (L = PPh3; R = Ph), and 3c (L = PPh3; R = C6H4‐NMe2‐4)] with methyllithium in THF at ‐78°C affords the alkylidyne acyl tungsten complexes Li[W(CR)(COMe)Br(CO)3L] [4b (L = CO; R = C6H4‐OMe‐4), 4c (L = CO, R = C6H4‐NMe2‐4), 5a (L = PPh3; R = Ph), and 5c (L = PPh3; R = C6H4‐NMe2‐4)]. Reaction of complexes 4 and 5 with C2O2Br2 at ‐78°C‐0°C in CH2Cl2 followed by addition of PPh3 gives the alkyne complexes [WBr2(CO)(CH3C = CR)(PPh3)2] (6). The formation of the alkyne ligands in complexes 6 may be considered as the result of formal coupling of two alkylidyne ligands.

AB - Reaction of the alkylidyne complexes [W(CR)Br(CO)3L] [2b (L = CO; R = C6H4‐OMe‐4), 2c (L = CO, R = C6H4‐NMe2‐4), 3a (L = PPh3; R = Ph), and 3c (L = PPh3; R = C6H4‐NMe2‐4)] with methyllithium in THF at ‐78°C affords the alkylidyne acyl tungsten complexes Li[W(CR)(COMe)Br(CO)3L] [4b (L = CO; R = C6H4‐OMe‐4), 4c (L = CO, R = C6H4‐NMe2‐4), 5a (L = PPh3; R = Ph), and 5c (L = PPh3; R = C6H4‐NMe2‐4)]. Reaction of complexes 4 and 5 with C2O2Br2 at ‐78°C‐0°C in CH2Cl2 followed by addition of PPh3 gives the alkyne complexes [WBr2(CO)(CH3C = CR)(PPh3)2] (6). The formation of the alkyne ligands in complexes 6 may be considered as the result of formal coupling of two alkylidyne ligands.

KW - Alkylidyne ligands

KW - Carbon–carbon coupling

KW - Tungsten complexes

UR - https://www.scopus.com/pages/publications/0000359848

U2 - 10.1002/cber.19921250712

DO - 10.1002/cber.19921250712

M3 - Article

AN - SCOPUS:0000359848

SN - 0009-2940

VL - 125

SP - 1583

EP - 1588

JO - Chemische Berichte

JF - Chemische Berichte

IS - 7

ER -

Formal coupling of two alkylidyne ligands on a metal center

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