Carbonylation and hydrogenation of cis-CH3Mn(CO)4L, substitutional reactivity of cis-HMn(CO)4L, and binuclear elimination between cis-CH3Mn(CO)4P(OPh)3 and cis-HMn(CO)4P(OPh)3(L = CO, PPh3, P(OPh)3, PBu3 and P(OMe)3)

Ronald J. Ruszczyk; Bih Lian Huang; Jim D. Atwood

doi:10.1016/0022-328X(86)82016-2

Carbonylation and hydrogenation of cis-CH₃Mn(CO)₄L, substitutional reactivity of cis-HMn(CO)₄L, and binuclear elimination between cis-CH₃Mn(CO)₄P(OPh)₃ and cis-HMn(CO)₄P(OPh)₃(L = CO, PPh₃, P(OPh)₃, PBu₃ and P(OMe)₃)

Ronald J. Ruszczyk
, Bih Lian Huang
, Jim D. Atwood

Chemistry

SUNY Buffalo

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

22 Scopus citations

Abstract

Several reactions of cis-CH₃Mn(CO)₄L and cis-HMn(CO)₄L, have been investigated. The carbonylation of cis-CH₃Mn(CO)₄L (L = CO, P(OPh)₃, P(OMe)₃ and PBu₃) shows only a very small ligand effect, indicating a transition state that has little unsaturation. Reaction with H₂ has very similar observed rate constants and activation parameters to the carbonylation. The hydrides, cis-HMn(CO)₄L (L = P(OPh)₃, PPh₃ and PBu₃), are remarkably unreactive toward substitution, requiring temperatures of 100°C. A radical mechanism is most likely. Reactions of cis-HMn(CO)₄P(OPh)₃ with cis-CH₃Mn(CO)₄P(OPh)₃ and cis-HMn(CO)₄PBu₃ with CH₃C(O)Mn(CO)₅ occur at temperatures where methyl migration is readily established and the hydride complexes are unreactive. Thus methyl migration, followed by coordination to a bridging hydride, is indicated for these binuclear reductive elimination reactions.

Original language	English
Pages (from-to)	205-211
Number of pages	7
Journal	Journal of Organometallic Chemistry
Volume	299
Issue number	2
DOIs	https://doi.org/10.1016/0022-328X(86)82016-2
State	Published - Jan 21 1986

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Ruszczyk, R. J., Huang, B. L., & Atwood, J. D. (1986). Carbonylation and hydrogenation of cis-CH₃Mn(CO)₄L, substitutional reactivity of cis-HMn(CO)₄L, and binuclear elimination between cis-CH₃Mn(CO)₄P(OPh)₃ and cis-HMn(CO)₄P(OPh)₃(L = CO, PPh₃, P(OPh)₃, PBu₃ and P(OMe)₃). Journal of Organometallic Chemistry, 299(2), 205-211. https://doi.org/10.1016/0022-328X(86)82016-2

@article{ef5b4e38730d42f4b9706e3fe9094416,

title = "Carbonylation and hydrogenation of cis-CH3Mn(CO)4L, substitutional reactivity of cis-HMn(CO)4L, and binuclear elimination between cis-CH3Mn(CO)4P(OPh)3 and cis-HMn(CO)4P(OPh)3(L = CO, PPh3, P(OPh)3, PBu3 and P(OMe)3)",

abstract = "Several reactions of cis-CH3Mn(CO)4L and cis-HMn(CO)4L, have been investigated. The carbonylation of cis-CH3Mn(CO)4L (L = CO, P(OPh)3, P(OMe)3 and PBu3) shows only a very small ligand effect, indicating a transition state that has little unsaturation. Reaction with H2 has very similar observed rate constants and activation parameters to the carbonylation. The hydrides, cis-HMn(CO)4L (L = P(OPh)3, PPh3 and PBu3), are remarkably unreactive toward substitution, requiring temperatures of 100°C. A radical mechanism is most likely. Reactions of cis-HMn(CO)4P(OPh)3 with cis-CH3Mn(CO)4P(OPh)3 and cis-HMn(CO)4PBu3 with CH3C(O)Mn(CO)5 occur at temperatures where methyl migration is readily established and the hydride complexes are unreactive. Thus methyl migration, followed by coordination to a bridging hydride, is indicated for these binuclear reductive elimination reactions.",

author = "Ruszczyk, \{Ronald J.\} and Huang, \{Bih Lian\} and Atwood, \{Jim D.\}",

year = "1986",

month = jan,

day = "21",

doi = "10.1016/0022-328X(86)82016-2",

language = "English",

volume = "299",

pages = "205--211",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "2",

}

Ruszczyk, RJ, Huang, BL & Atwood, JD 1986, 'Carbonylation and hydrogenation of cis-CH₃Mn(CO)₄L, substitutional reactivity of cis-HMn(CO)₄L, and binuclear elimination between cis-CH₃Mn(CO)₄P(OPh)₃ and cis-HMn(CO)₄P(OPh)₃(L = CO, PPh₃, P(OPh)₃, PBu₃ and P(OMe)₃)', Journal of Organometallic Chemistry, vol. 299, no. 2, pp. 205-211. https://doi.org/10.1016/0022-328X(86)82016-2

Carbonylation and hydrogenation of cis-CH₃Mn(CO)₄L, substitutional reactivity of cis-HMn(CO)₄L, and binuclear elimination between cis-CH₃Mn(CO)₄P(OPh)₃ and cis-HMn(CO)₄P(OPh)₃(L = CO, PPh₃, P(OPh)₃, PBu₃ and P(OMe)₃). / Ruszczyk, Ronald J.; Huang, Bih Lian; Atwood, Jim D.
In: Journal of Organometallic Chemistry, Vol. 299, No. 2, 21.01.1986, p. 205-211.

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

TY - JOUR

T1 - Carbonylation and hydrogenation of cis-CH3Mn(CO)4L, substitutional reactivity of cis-HMn(CO)4L, and binuclear elimination between cis-CH3Mn(CO)4P(OPh)3 and cis-HMn(CO)4P(OPh)3(L = CO, PPh3, P(OPh)3, PBu3 and P(OMe)3)

AU - Ruszczyk, Ronald J.

AU - Huang, Bih Lian

AU - Atwood, Jim D.

PY - 1986/1/21

Y1 - 1986/1/21

N2 - Several reactions of cis-CH3Mn(CO)4L and cis-HMn(CO)4L, have been investigated. The carbonylation of cis-CH3Mn(CO)4L (L = CO, P(OPh)3, P(OMe)3 and PBu3) shows only a very small ligand effect, indicating a transition state that has little unsaturation. Reaction with H2 has very similar observed rate constants and activation parameters to the carbonylation. The hydrides, cis-HMn(CO)4L (L = P(OPh)3, PPh3 and PBu3), are remarkably unreactive toward substitution, requiring temperatures of 100°C. A radical mechanism is most likely. Reactions of cis-HMn(CO)4P(OPh)3 with cis-CH3Mn(CO)4P(OPh)3 and cis-HMn(CO)4PBu3 with CH3C(O)Mn(CO)5 occur at temperatures where methyl migration is readily established and the hydride complexes are unreactive. Thus methyl migration, followed by coordination to a bridging hydride, is indicated for these binuclear reductive elimination reactions.

AB - Several reactions of cis-CH3Mn(CO)4L and cis-HMn(CO)4L, have been investigated. The carbonylation of cis-CH3Mn(CO)4L (L = CO, P(OPh)3, P(OMe)3 and PBu3) shows only a very small ligand effect, indicating a transition state that has little unsaturation. Reaction with H2 has very similar observed rate constants and activation parameters to the carbonylation. The hydrides, cis-HMn(CO)4L (L = P(OPh)3, PPh3 and PBu3), are remarkably unreactive toward substitution, requiring temperatures of 100°C. A radical mechanism is most likely. Reactions of cis-HMn(CO)4P(OPh)3 with cis-CH3Mn(CO)4P(OPh)3 and cis-HMn(CO)4PBu3 with CH3C(O)Mn(CO)5 occur at temperatures where methyl migration is readily established and the hydride complexes are unreactive. Thus methyl migration, followed by coordination to a bridging hydride, is indicated for these binuclear reductive elimination reactions.

UR - https://www.scopus.com/pages/publications/0346021888

U2 - 10.1016/0022-328X(86)82016-2

DO - 10.1016/0022-328X(86)82016-2

M3 - Article

AN - SCOPUS:0346021888

SN - 0022-328X

VL - 299

SP - 205

EP - 211

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 2