Synthesis and Reactivity of Trans Isomers of Bls(phosphine)-substituted Carbyne Complexes of Molybdenum and Tungsten: [M(=CR)x(CO)2(PR3)2]

Andreas Mayr; Michael A. Kjelsberg; Ken S. Lee; Marianna F. Asaro; Tze chen Hsieh

doi:10.1021/om00155a030

Synthesis and Reactivity of Trans Isomers of Bls(phosphine)-substituted Carbyne Complexes of Molybdenum and Tungsten: [M(=CR)x(CO)₂(PR₃)₂]

Andreas Mayr
, Michael A. Kjelsberg
, Ken S. Lee
, Marianna F. Asaro
, Tze chen Hsieh

Chemistry

Stony Brook University

Princeton University

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

22 Scopus citations

Abstract

Irradiation with visible light of the cis bis-(phosphine)-substituted molybdenum and tungsten carbyne complexes cis,cis-[MΞ(CPh)X(CO)₂(PR₃)₂] generates the trans isomers. The isomerization is postulated to proceed via photogenerated pentacoordinate metal ketenyl complexes. Irradiation of cis,cis-[W(ΞCPh)X-(CO)₂(PMe₃)₂] at low temperatures In the presence of PMe₃and PhCCH results in formation of the thermally labile tungsten ketenyl complexes [W(η²-PhCCO)CI-(CO)(PMe₃)₃] and [W(η¹-PhCCO)Cl(CO)(PhCCH)(PMe₃)₂], respectively. Substitution of one carbonyl ligand in the trans bis(phosphine)-substituted metal carbyne complexes is demonstrated.

Original language	English
Pages (from-to)	2610-2612
Number of pages	3
Journal	Organometallics
Volume	6
Issue number	12
DOIs	https://doi.org/10.1021/om00155a030
State	Published - Dec 1 1987

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@article{a1b428d675c4454fa36b65bd27762c49,

title = "Synthesis and Reactivity of Trans Isomers of Bls(phosphine)-substituted Carbyne Complexes of Molybdenum and Tungsten: [M(=CR)x(CO)2(PR3)2]",

abstract = "Irradiation with visible light of the cis bis-(phosphine)-substituted molybdenum and tungsten carbyne complexes cis,cis-[MΞ(CPh)X(CO)2(PR3)2] generates the trans isomers. The isomerization is postulated to proceed via photogenerated pentacoordinate metal ketenyl complexes. Irradiation of cis,cis-[W(ΞCPh)X-(CO)2(PMe3)2] at low temperatures In the presence of PMe3and PhCCH results in formation of the thermally labile tungsten ketenyl complexes [W(η2-PhCCO)CI-(CO)(PMe3)3] and [W(η1-PhCCO)Cl(CO)(PhCCH)(PMe3)2], respectively. Substitution of one carbonyl ligand in the trans bis(phosphine)-substituted metal carbyne complexes is demonstrated.",

author = "Andreas Mayr and Kjelsberg, \{Michael A.\} and Lee, \{Ken S.\} and Asaro, \{Marianna F.\} and Hsieh, \{Tze chen\}",

year = "1987",

month = dec,

day = "1",

doi = "10.1021/om00155a030",

language = "English",

volume = "6",

pages = "2610--2612",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "12",

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TY - JOUR

T1 - Synthesis and Reactivity of Trans Isomers of Bls(phosphine)-substituted Carbyne Complexes of Molybdenum and Tungsten

T2 - [M(=CR)x(CO)2(PR3)2]

AU - Mayr, Andreas

AU - Kjelsberg, Michael A.

AU - Lee, Ken S.

AU - Asaro, Marianna F.

AU - Hsieh, Tze chen

PY - 1987/12/1

Y1 - 1987/12/1

N2 - Irradiation with visible light of the cis bis-(phosphine)-substituted molybdenum and tungsten carbyne complexes cis,cis-[MΞ(CPh)X(CO)2(PR3)2] generates the trans isomers. The isomerization is postulated to proceed via photogenerated pentacoordinate metal ketenyl complexes. Irradiation of cis,cis-[W(ΞCPh)X-(CO)2(PMe3)2] at low temperatures In the presence of PMe3and PhCCH results in formation of the thermally labile tungsten ketenyl complexes [W(η2-PhCCO)CI-(CO)(PMe3)3] and [W(η1-PhCCO)Cl(CO)(PhCCH)(PMe3)2], respectively. Substitution of one carbonyl ligand in the trans bis(phosphine)-substituted metal carbyne complexes is demonstrated.

AB - Irradiation with visible light of the cis bis-(phosphine)-substituted molybdenum and tungsten carbyne complexes cis,cis-[MΞ(CPh)X(CO)2(PR3)2] generates the trans isomers. The isomerization is postulated to proceed via photogenerated pentacoordinate metal ketenyl complexes. Irradiation of cis,cis-[W(ΞCPh)X-(CO)2(PMe3)2] at low temperatures In the presence of PMe3and PhCCH results in formation of the thermally labile tungsten ketenyl complexes [W(η2-PhCCO)CI-(CO)(PMe3)3] and [W(η1-PhCCO)Cl(CO)(PhCCH)(PMe3)2], respectively. Substitution of one carbonyl ligand in the trans bis(phosphine)-substituted metal carbyne complexes is demonstrated.

UR - https://www.scopus.com/pages/publications/0010942482

U2 - 10.1021/om00155a030

DO - 10.1021/om00155a030

M3 - Article

SN - 0276-7333

VL - 6

SP - 2610

EP - 2612

JO - Organometallics

JF - Organometallics

IS - 12

ER -

Synthesis and Reactivity of Trans Isomers of Bls(phosphine)-substituted Carbyne Complexes of Molybdenum and Tungsten: [M(=CR)x(CO)₂(PR₃)₂]

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