Facile Interconversions of Alkyne and Vinylidene Ligands on Divalent Molybdenum and Tungsten

Peter N. Nicklas; John P. Selegue; Bruce A. Young

doi:10.1021/om00100a034

Facile Interconversions of Alkyne and Vinylidene Ligands on Divalent Molybdenum and Tungsten

Peter N. Nicklas, John P. Selegue, Bruce A. Young

Chemistry

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Abstract

Molybdenum alkynyls trans-[M(C≡CCMe₃)L-(PR₃)₂(Cp)] (7, 8, 12) are prepared by deprotonation of [Mo(HC≡CCMe₃)(PR₃)₂(Cp)]⁺(5, PR₃ = P(OMe)₃; 6, PR₃ = PMe₂Ph) using NaN(SiMe₃)₂ in the presence of CO (7 and 8) or P(OMe)₃ (12). Protonation of [Mo(C≡CMe₃)-(CO){P(OMe)₃}₂(Cp)] (7) at -78 °C gives frans-[Mo(C= CHCMe₃)(CO){P(OMe)₃}₂(Cp)] [X] (9), which decarbonylates to 5 above 0 °C (X = BF₄) or is trapped by excess triflic acid (HOTf) to give the alkylidyne complex trans-[Mo(≡CCH₂CMe₃(OTf){P(OMe)₃}₂(Cp)][OTf] (11). Protonation of [Mo(C≡CCMe₃(CO)(PMe₂Ph)₂(Cp)] (8) with HOTf gives stable trans-[Mo(C=CHCMe₃)(CO)-(PMe₂Ph)₂(Cp)] [OTf] (10), while exposure of [Mo(HC≡CCMe₃)(PMe₂Ph)₂(Cp)] [BF₄] (6) to 1 atm of CO effects its conversion to trans-[Mo(C=CHCMe₃)(CO)(PMe₂Ph)₂-(Cp)][BF₄] (10). The structure of trans-[W(C= CMePh)(CO){P(OMe)₃}₂(Cp)] [PF₆] (4) was determined by X-ray diffraction (R = 3.3%, R_w = 4.0%).

Original language	English
Pages (from-to)	2248-2250
Number of pages	3
Journal	Organometallics
Volume	7
Issue number	10
DOIs	https://doi.org/10.1021/om00100a034
State	Published - Oct 1988

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om00100a034

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@article{815c19b9fadb48feb4d7908cf2ad933f,

title = "Facile Interconversions of Alkyne and Vinylidene Ligands on Divalent Molybdenum and Tungsten",

abstract = "Molybdenum alkynyls trans-[M(C≡CCMe3)L-(PR3)2(Cp)] (7, 8, 12) are prepared by deprotonation of [Mo(HC≡CCMe3)(PR3)2(Cp)]+(5, PR3 = P(OMe)3; 6, PR3 = PMe2Ph) using NaN(SiMe3)2 in the presence of CO (7 and 8) or P(OMe)3 (12). Protonation of [Mo(C≡CMe3)-(CO){P(OMe)3}2(Cp)] (7) at -78 °C gives frans-[Mo(C= CHCMe3)(CO){P(OMe)3}2(Cp)] [X] (9), which decarbonylates to 5 above 0 °C (X = BF4) or is trapped by excess triflic acid (HOTf) to give the alkylidyne complex trans-[Mo(≡CCH2CMe3(OTf){P(OMe)3}2(Cp)][OTf] (11). Protonation of [Mo(C≡CCMe3(CO)(PMe2Ph)2(Cp)] (8) with HOTf gives stable trans-[Mo(C=CHCMe3)(CO)-(PMe2Ph)2(Cp)] [OTf] (10), while exposure of [Mo(HC≡CCMe3)(PMe2Ph)2(Cp)] [BF4] (6) to 1 atm of CO effects its conversion to trans-[Mo(C=CHCMe3)(CO)(PMe2Ph)2-(Cp)][BF4] (10). The structure of trans-[W(C= CMePh)(CO){P(OMe)3}2(Cp)] [PF6] (4) was determined by X-ray diffraction (R = 3.3%, Rw = 4.0%).",

author = "Nicklas, {Peter N.} and Selegue, {John P.} and Young, {Bruce A.}",

year = "1988",

month = oct,

doi = "10.1021/om00100a034",

language = "English",

volume = "7",

pages = "2248--2250",

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T1 - Facile Interconversions of Alkyne and Vinylidene Ligands on Divalent Molybdenum and Tungsten

AU - Nicklas, Peter N.

AU - Selegue, John P.

AU - Young, Bruce A.

PY - 1988/10

Y1 - 1988/10

N2 - Molybdenum alkynyls trans-[M(C≡CCMe3)L-(PR3)2(Cp)] (7, 8, 12) are prepared by deprotonation of [Mo(HC≡CCMe3)(PR3)2(Cp)]+(5, PR3 = P(OMe)3; 6, PR3 = PMe2Ph) using NaN(SiMe3)2 in the presence of CO (7 and 8) or P(OMe)3 (12). Protonation of [Mo(C≡CMe3)-(CO){P(OMe)3}2(Cp)] (7) at -78 °C gives frans-[Mo(C= CHCMe3)(CO){P(OMe)3}2(Cp)] [X] (9), which decarbonylates to 5 above 0 °C (X = BF4) or is trapped by excess triflic acid (HOTf) to give the alkylidyne complex trans-[Mo(≡CCH2CMe3(OTf){P(OMe)3}2(Cp)][OTf] (11). Protonation of [Mo(C≡CCMe3(CO)(PMe2Ph)2(Cp)] (8) with HOTf gives stable trans-[Mo(C=CHCMe3)(CO)-(PMe2Ph)2(Cp)] [OTf] (10), while exposure of [Mo(HC≡CCMe3)(PMe2Ph)2(Cp)] [BF4] (6) to 1 atm of CO effects its conversion to trans-[Mo(C=CHCMe3)(CO)(PMe2Ph)2-(Cp)][BF4] (10). The structure of trans-[W(C= CMePh)(CO){P(OMe)3}2(Cp)] [PF6] (4) was determined by X-ray diffraction (R = 3.3%, Rw = 4.0%).

AB - Molybdenum alkynyls trans-[M(C≡CCMe3)L-(PR3)2(Cp)] (7, 8, 12) are prepared by deprotonation of [Mo(HC≡CCMe3)(PR3)2(Cp)]+(5, PR3 = P(OMe)3; 6, PR3 = PMe2Ph) using NaN(SiMe3)2 in the presence of CO (7 and 8) or P(OMe)3 (12). Protonation of [Mo(C≡CMe3)-(CO){P(OMe)3}2(Cp)] (7) at -78 °C gives frans-[Mo(C= CHCMe3)(CO){P(OMe)3}2(Cp)] [X] (9), which decarbonylates to 5 above 0 °C (X = BF4) or is trapped by excess triflic acid (HOTf) to give the alkylidyne complex trans-[Mo(≡CCH2CMe3(OTf){P(OMe)3}2(Cp)][OTf] (11). Protonation of [Mo(C≡CCMe3(CO)(PMe2Ph)2(Cp)] (8) with HOTf gives stable trans-[Mo(C=CHCMe3)(CO)-(PMe2Ph)2(Cp)] [OTf] (10), while exposure of [Mo(HC≡CCMe3)(PMe2Ph)2(Cp)] [BF4] (6) to 1 atm of CO effects its conversion to trans-[Mo(C=CHCMe3)(CO)(PMe2Ph)2-(Cp)][BF4] (10). The structure of trans-[W(C= CMePh)(CO){P(OMe)3}2(Cp)] [PF6] (4) was determined by X-ray diffraction (R = 3.3%, Rw = 4.0%).

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Facile Interconversions of Alkyne and Vinylidene Ligands on Divalent Molybdenum and Tungsten

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