Dangling phosphine complexes: Phosphine exchange in pentacarbonyl tungsten complexes of bis(diphenylphosphinomethyl)phenylphosphine

Chaminda P. Gamage; Ryan C. Bailey; Ellen A. Keiter; John R. Kuczynski; Kraig A. Wheeler; Charlotte L. Stern; Douglas E. Brandt; Richard L. Keiter

doi:10.1016/j.jorganchem.2015.07.017

Dangling phosphine complexes: Phosphine exchange in pentacarbonyl tungsten complexes of bis(diphenylphosphinomethyl)phenylphosphine

Chaminda P. Gamage, Ryan C. Bailey, Ellen A. Keiter, John R. Kuczynski, Kraig A. Wheeler, Charlotte L. Stern, Douglas E. Brandt, Richard L. Keiter

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

Abstract

Abstract The reaction of [W(CO)₅NH₂Ph] with Ph₂PCH₂PPhCH₂PPh₂ under mild conditions and stoichiometric control leads to two sets of linkage isomers: [(OC)₅W{κ¹-PPh(CH₂PPh₂)₂}] 6a and [(OC)₅W(κ¹- PPh₂CH₂PPhCH₂PPh₂)] 6b; [(OC)₅W{μ-PPh₂CH₂PPh(CH₂PPh₂)}W(CO)₅] 7a and [(OC)₅W(μ-PPh₂CH₂PPhCH₂PPh₂)W(CO)₅] 7b. Isomers 6a and 6b exist in solution in equilibrium with K = 4.35 for 6b/6a in CDCl₃ at 55 °C. Under the same conditions, the rate of isomerization of 6a to 6b is 4.32 × 10^-6 s^-1. Isomerization is thought to proceed by an initial attack of a carbonyl group by a pendant phosphine followed by ring opening and a 1,2-phosphine shift. At higher temperatures, chelated complexes with four- and six-membered rings are formed: [(OC)₅W{μ-κ¹-, κ²-PPh₂CH₂ (PhPCH₂PPh₂)W(CO)₄ }] 9a, [(OC)₅W{μ-κ¹-, κ²-PPh (CH₂PPh₂)₂}W(CO)₄ }] 9b, and [(OC)₄W{κ²-(PPh₂CH₂)₂PPh}] 10b. X-ray crystal structures of 6a, 7b, and 9b have been determined.

Original language	English (US)
Article number	19161
Pages (from-to)	258-265
Number of pages	8
Journal	Journal of Organometallic Chemistry
Volume	794
DOIs	https://doi.org/10.1016/j.jorganchem.2015.07.017
State	Published - Jul 27 2015

Keywords

Group 6 carbonyls
Linkage isomers
Pendant phosphines
Phosphine exchange
bis(diphenylphosphinomethyl)phenylphosphine

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Online availability

10.1016/j.jorganchem.2015.07.017

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Gamage, C. P., Bailey, R. C., Keiter, E. A., Kuczynski, J. R., Wheeler, K. A., Stern, C. L., Brandt, D. E., & Keiter, R. L. (2015). Dangling phosphine complexes: Phosphine exchange in pentacarbonyl tungsten complexes of bis(diphenylphosphinomethyl)phenylphosphine. Journal of Organometallic Chemistry, 794, 258-265. Article 19161. https://doi.org/10.1016/j.jorganchem.2015.07.017

@article{832987de981f4da480d5c308f428f17c,

title = "Dangling phosphine complexes: Phosphine exchange in pentacarbonyl tungsten complexes of bis(diphenylphosphinomethyl)phenylphosphine",

abstract = "Abstract The reaction of [W(CO)5NH2Ph] with Ph2PCH2PPhCH2PPh2 under mild conditions and stoichiometric control leads to two sets of linkage isomers: [(OC)5W{κ1-PPh(CH2PPh2)2}] 6a and [(OC)5W(κ1- PPh2CH2PPhCH2PPh2)] 6b; [(OC)5W{μ-PPh2CH2PPh(CH2PPh2)}W(CO)5] 7a and [(OC)5W(μ-PPh2CH2PPhCH2PPh2)W(CO)5] 7b. Isomers 6a and 6b exist in solution in equilibrium with K = 4.35 for 6b/6a in CDCl3 at 55 °C. Under the same conditions, the rate of isomerization of 6a to 6b is 4.32 × 10-6 s-1. Isomerization is thought to proceed by an initial attack of a carbonyl group by a pendant phosphine followed by ring opening and a 1,2-phosphine shift. At higher temperatures, chelated complexes with four- and six-membered rings are formed: [(OC)5W{μ-κ1-, κ2-PPh2CH2 (PhPCH2PPh2)W(CO)4 }] 9a, [(OC)5W{μ-κ1-, κ2-PPh (CH2PPh2)2}W(CO)4 }] 9b, and [(OC)4W{κ2-(PPh2CH2)2PPh}] 10b. X-ray crystal structures of 6a, 7b, and 9b have been determined.",

keywords = "Group 6 carbonyls, Linkage isomers, Pendant phosphines, Phosphine exchange, bis(diphenylphosphinomethyl)phenylphosphine",

author = "Gamage, {Chaminda P.} and Bailey, {Ryan C.} and Keiter, {Ellen A.} and Kuczynski, {John R.} and Wheeler, {Kraig A.} and Stern, {Charlotte L.} and Brandt, {Douglas E.} and Keiter, {Richard L.}",

note = "We thank the U. S. National Science Foundation ( CHE-136423 ) and the Camille and Henry Dreyfus Foundation ( SF-98-004 ) for support of this work.",

year = "2015",

month = jul,

day = "27",

doi = "10.1016/j.jorganchem.2015.07.017",

language = "English (US)",

volume = "794",

pages = "258--265",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

}

TY - JOUR

T1 - Dangling phosphine complexes

T2 - Phosphine exchange in pentacarbonyl tungsten complexes of bis(diphenylphosphinomethyl)phenylphosphine

AU - Gamage, Chaminda P.

AU - Bailey, Ryan C.

AU - Keiter, Ellen A.

AU - Kuczynski, John R.

AU - Wheeler, Kraig A.

AU - Stern, Charlotte L.

AU - Brandt, Douglas E.

AU - Keiter, Richard L.

N1 - We thank the U. S. National Science Foundation ( CHE-136423 ) and the Camille and Henry Dreyfus Foundation ( SF-98-004 ) for support of this work.

PY - 2015/7/27

Y1 - 2015/7/27

N2 - Abstract The reaction of [W(CO)5NH2Ph] with Ph2PCH2PPhCH2PPh2 under mild conditions and stoichiometric control leads to two sets of linkage isomers: [(OC)5W{κ1-PPh(CH2PPh2)2}] 6a and [(OC)5W(κ1- PPh2CH2PPhCH2PPh2)] 6b; [(OC)5W{μ-PPh2CH2PPh(CH2PPh2)}W(CO)5] 7a and [(OC)5W(μ-PPh2CH2PPhCH2PPh2)W(CO)5] 7b. Isomers 6a and 6b exist in solution in equilibrium with K = 4.35 for 6b/6a in CDCl3 at 55 °C. Under the same conditions, the rate of isomerization of 6a to 6b is 4.32 × 10-6 s-1. Isomerization is thought to proceed by an initial attack of a carbonyl group by a pendant phosphine followed by ring opening and a 1,2-phosphine shift. At higher temperatures, chelated complexes with four- and six-membered rings are formed: [(OC)5W{μ-κ1-, κ2-PPh2CH2 (PhPCH2PPh2)W(CO)4 }] 9a, [(OC)5W{μ-κ1-, κ2-PPh (CH2PPh2)2}W(CO)4 }] 9b, and [(OC)4W{κ2-(PPh2CH2)2PPh}] 10b. X-ray crystal structures of 6a, 7b, and 9b have been determined.

AB - Abstract The reaction of [W(CO)5NH2Ph] with Ph2PCH2PPhCH2PPh2 under mild conditions and stoichiometric control leads to two sets of linkage isomers: [(OC)5W{κ1-PPh(CH2PPh2)2}] 6a and [(OC)5W(κ1- PPh2CH2PPhCH2PPh2)] 6b; [(OC)5W{μ-PPh2CH2PPh(CH2PPh2)}W(CO)5] 7a and [(OC)5W(μ-PPh2CH2PPhCH2PPh2)W(CO)5] 7b. Isomers 6a and 6b exist in solution in equilibrium with K = 4.35 for 6b/6a in CDCl3 at 55 °C. Under the same conditions, the rate of isomerization of 6a to 6b is 4.32 × 10-6 s-1. Isomerization is thought to proceed by an initial attack of a carbonyl group by a pendant phosphine followed by ring opening and a 1,2-phosphine shift. At higher temperatures, chelated complexes with four- and six-membered rings are formed: [(OC)5W{μ-κ1-, κ2-PPh2CH2 (PhPCH2PPh2)W(CO)4 }] 9a, [(OC)5W{μ-κ1-, κ2-PPh (CH2PPh2)2}W(CO)4 }] 9b, and [(OC)4W{κ2-(PPh2CH2)2PPh}] 10b. X-ray crystal structures of 6a, 7b, and 9b have been determined.

KW - Group 6 carbonyls

KW - Linkage isomers

KW - Pendant phosphines

KW - Phosphine exchange

KW - bis(diphenylphosphinomethyl)phenylphosphine

UR - http://www.scopus.com/inward/record.url?scp=84937821902&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84937821902&partnerID=8YFLogxK

U2 - 10.1016/j.jorganchem.2015.07.017

DO - 10.1016/j.jorganchem.2015.07.017

M3 - Article

AN - SCOPUS:84937821902

SN - 0022-328X

VL - 794

SP - 258

EP - 265

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

M1 - 19161

ER -

Dangling phosphine complexes: Phosphine exchange in pentacarbonyl tungsten complexes of bis(diphenylphosphinomethyl)phenylphosphine

Abstract

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