Alkynyl selenolate complexes of iron, nickel, and molybdenum

Lorraine M. Caldwell; Anthony F. Hill; Alexander G. Hulkes; Caitlin M.A. McQueen; Andrew J.P. White; David J. Williams

doi:10.1021/om100694f

Alkynyl selenolate complexes of iron, nickel, and molybdenum

Lorraine M. Caldwell, Anthony F. Hill, Alexander G. Hulkes, Caitlin M.A. McQueen, Andrew J.P. White, David J. Williams

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Abstract

The successive treatment of terminal alkynes, HC≡CR (R = C ₆H₄Me-4, SiMe₃), with ⁿBuLi and gray selenium affords LiSeC≡CR, which in turn reacts with [FeCl(CO) ₂(η-C₅H₅)], [NiCl(PPh₃)(η- C₅H₅)], and [MoI(CO)₃(η-C₅H ₅)] to afford the alkynylselenolato complexes [Fe(SeC≡CR)(CO) ₂(η-C₅H₅)], [Ni(SeC≡CR)(PPh ₃)(η-C₅H₅)], and [Mo(SeC≡CR)(CO) ₃(η-C₅H₅)], two examples of which have been structurally characterized. When [MoI(CO)₃{HB(pz)₃}] (pz = pyrazol-1-yl) was however employed as the electrophile, low yields of the selenoketenyl complex [Mo(η²-C,C′-SeCCR)(CO) ₂{HB(pz)₃}] were obtained via the presumed intermediacy of the alkynylselenolato complex [Mo(σ-SeC≡CR)(CO)₃{HB(pz) ₃}], which is perhaps destabilized relative to the selenoketenyl complex by the octahedral enforcer character of the HB(pz)₃ ligand.

Original language	English
Pages (from-to)	6350-6358
Number of pages	9
Journal	Organometallics
Volume	29
Issue number	23
DOIs	https://doi.org/10.1021/om100694f
Publication status	Published - 13 Dec 2010

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@article{9a658963d4d340bc8b16ad3ceb1f42e6,

title = "Alkynyl selenolate complexes of iron, nickel, and molybdenum",

abstract = "The successive treatment of terminal alkynes, HC≡CR (R = C 6H4Me-4, SiMe3), with nBuLi and gray selenium affords LiSeC≡CR, which in turn reacts with [FeCl(CO) 2(η-C5H5)], [NiCl(PPh3)(η- C5H5)], and [MoI(CO)3(η-C5H 5)] to afford the alkynylselenolato complexes [Fe(SeC≡CR)(CO) 2(η-C5H5)], [Ni(SeC≡CR)(PPh 3)(η-C5H5)], and [Mo(SeC≡CR)(CO) 3(η-C5H5)], two examples of which have been structurally characterized. When [MoI(CO)3{HB(pz)3}] (pz = pyrazol-1-yl) was however employed as the electrophile, low yields of the selenoketenyl complex [Mo(η2-C,C′-SeCCR)(CO) 2{HB(pz)3}] were obtained via the presumed intermediacy of the alkynylselenolato complex [Mo(σ-SeC≡CR)(CO)3{HB(pz) 3}], which is perhaps destabilized relative to the selenoketenyl complex by the octahedral enforcer character of the HB(pz)3 ligand.",

author = "Caldwell, {Lorraine M.} and Hill, {Anthony F.} and Hulkes, {Alexander G.} and McQueen, {Caitlin M.A.} and White, {Andrew J.P.} and Williams, {David J.}",

year = "2010",

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language = "English",

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T1 - Alkynyl selenolate complexes of iron, nickel, and molybdenum

AU - Caldwell, Lorraine M.

AU - Hill, Anthony F.

AU - Hulkes, Alexander G.

AU - McQueen, Caitlin M.A.

AU - White, Andrew J.P.

AU - Williams, David J.

PY - 2010/12/13

Y1 - 2010/12/13

N2 - The successive treatment of terminal alkynes, HC≡CR (R = C 6H4Me-4, SiMe3), with nBuLi and gray selenium affords LiSeC≡CR, which in turn reacts with [FeCl(CO) 2(η-C5H5)], [NiCl(PPh3)(η- C5H5)], and [MoI(CO)3(η-C5H 5)] to afford the alkynylselenolato complexes [Fe(SeC≡CR)(CO) 2(η-C5H5)], [Ni(SeC≡CR)(PPh 3)(η-C5H5)], and [Mo(SeC≡CR)(CO) 3(η-C5H5)], two examples of which have been structurally characterized. When [MoI(CO)3{HB(pz)3}] (pz = pyrazol-1-yl) was however employed as the electrophile, low yields of the selenoketenyl complex [Mo(η2-C,C′-SeCCR)(CO) 2{HB(pz)3}] were obtained via the presumed intermediacy of the alkynylselenolato complex [Mo(σ-SeC≡CR)(CO)3{HB(pz) 3}], which is perhaps destabilized relative to the selenoketenyl complex by the octahedral enforcer character of the HB(pz)3 ligand.

AB - The successive treatment of terminal alkynes, HC≡CR (R = C 6H4Me-4, SiMe3), with nBuLi and gray selenium affords LiSeC≡CR, which in turn reacts with [FeCl(CO) 2(η-C5H5)], [NiCl(PPh3)(η- C5H5)], and [MoI(CO)3(η-C5H 5)] to afford the alkynylselenolato complexes [Fe(SeC≡CR)(CO) 2(η-C5H5)], [Ni(SeC≡CR)(PPh 3)(η-C5H5)], and [Mo(SeC≡CR)(CO) 3(η-C5H5)], two examples of which have been structurally characterized. When [MoI(CO)3{HB(pz)3}] (pz = pyrazol-1-yl) was however employed as the electrophile, low yields of the selenoketenyl complex [Mo(η2-C,C′-SeCCR)(CO) 2{HB(pz)3}] were obtained via the presumed intermediacy of the alkynylselenolato complex [Mo(σ-SeC≡CR)(CO)3{HB(pz) 3}], which is perhaps destabilized relative to the selenoketenyl complex by the octahedral enforcer character of the HB(pz)3 ligand.

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U2 - 10.1021/om100694f

DO - 10.1021/om100694f

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JO - Organometallics

JF - Organometallics

IS - 23

ER -

Alkynyl selenolate complexes of iron, nickel, and molybdenum

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