An η2 transition state for the insertion of M(PR3)2 fragments (M = Pd or Pt) into the phosphorus-carbon bonds of pentacarbonyl(phosphirane)tungsten complexes

Duncan Carmichael; Peter B. Hitchcock; John F. Nixon; François Mathey; Louis Ricard

doi:10.1039/DT9930001811

An η² transition state for the insertion of M(PR₃)₂ fragments (M = Pd or Pt) into the phosphorus-carbon bonds of pentacarbonyl(phosphirane)tungsten complexes

Duncan Carmichael
, Peter B. Hitchcock
, John F. Nixon
, François Mathey
, Louis Ricard

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

Abstract

The reaction of (E)- and (Z)-[W(CO)₅(PPhCHPhCHPh)] complexes with [M(PR₃)₂(C₂H₄)] [M = Pd, (PR₃)₂ = dppe (Ph₂PCH₂CH₂PPh₂); M = Pt, PR₃ = PPh₃] has been studied and the following products [which result from insertion of the M(PR₃)₂ frogment into the phosphirane ring] have been fully characterised by NMR spectroscopy: (2R*,3S*,4S*)-(±)-, (2R*,3S*,4R*)-(±)- and (2R*,3S*,4R*)-(±)-[(dppe) Pd(CHPhCHPhPPh)W(CO)₅]; (2S*,3S*,4S*)-(±)-, (2S*3R*4R*)-(±)- and (2S*,3S*,4R*)-(±)-[(Ph₃P) ₂Pt(CHPhCHPhPPh)W(CO)₅]; and trans-(2S*,3S*,4R*)-(±)-[(Ph ₃P)(OC)Pt-(CHPhCHPhPPh)W(CO)₅]. The crystal and molecular structures of (Z)-[W(CO)₅(PPhCHPhCHPh)], (2R*,3S*,4R*)-(±)- and (R*,3S*,4S*)-(±)-[(dppe)Pd(CHPhCHPhPPh)W(CO) ₅] have been determined. The configurations of the products are interpreted in terms of a transition state in which a P-C bond is η²-co-ordinated to M(PR₃)₂ fragment.

Original language	English
Pages (from-to)	1811-1822
Number of pages	12
Journal	Journal of the Chemical Society - Dalton Transactions
Issue number	12
DOIs	https://doi.org/10.1039/DT9930001811
Publication status	Published - 1 Dec 1993
Externally published	Yes

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@article{cfbbca88309942a5a50b2df1aeec2f92,

title = "An η2 transition state for the insertion of M(PR3)2 fragments (M = Pd or Pt) into the phosphorus-carbon bonds of pentacarbonyl(phosphirane)tungsten complexes",

abstract = "The reaction of (E)- and (Z)-[W(CO)5(PPhCHPhCHPh)] complexes with [M(PR3)2(C2H4)] [M = Pd, (PR3)2 = dppe (Ph2PCH2CH2PPh2); M = Pt, PR3 = PPh3] has been studied and the following products [which result from insertion of the M(PR3)2 frogment into the phosphirane ring] have been fully characterised by NMR spectroscopy: (2R*,3S*,4S*)-(±)-, (2R*,3S*,4R*)-(±)- and (2R*,3S*,4R*)-(±)-[(dppe) Pd(CHPhCHPhPPh)W(CO)5]; (2S*,3S*,4S*)-(±)-, (2S*3R*4R*)-(±)- and (2S*,3S*,4R*)-(±)-[(Ph3P) 2Pt(CHPhCHPhPPh)W(CO)5]; and trans-(2S*,3S*,4R*)-(±)-[(Ph 3P)(OC)Pt-(CHPhCHPhPPh)W(CO)5]. The crystal and molecular structures of (Z)-[W(CO)5(PPhCHPhCHPh)], (2R*,3S*,4R*)-(±)- and (R*,3S*,4S*)-(±)-[(dppe)Pd(CHPhCHPhPPh)W(CO) 5] have been determined. The configurations of the products are interpreted in terms of a transition state in which a P-C bond is η2-co-ordinated to M(PR3)2 fragment.",

author = "Duncan Carmichael and Hitchcock, \{Peter B.\} and Nixon, \{John F.\} and Fran{\c c}ois Mathey and Louis Ricard",

year = "1993",

month = dec,

day = "1",

doi = "10.1039/DT9930001811",

language = "English",

pages = "1811--1822",

journal = "Journal of the Chemical Society - Dalton Transactions",

issn = "0300-9246",

number = "12",

}

An η² transition state for the insertion of M(PR₃)₂ fragments (M = Pd or Pt) into the phosphorus-carbon bonds of pentacarbonyl(phosphirane)tungsten complexes. / Carmichael, Duncan; Hitchcock, Peter B.; Nixon, John F. et al.
In: Journal of the Chemical Society - Dalton Transactions, No. 12, 01.12.1993, p. 1811-1822.

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

TY - JOUR

T1 - An η2 transition state for the insertion of M(PR3)2 fragments (M = Pd or Pt) into the phosphorus-carbon bonds of pentacarbonyl(phosphirane)tungsten complexes

AU - Carmichael, Duncan

AU - Hitchcock, Peter B.

AU - Nixon, John F.

AU - Mathey, François

AU - Ricard, Louis

PY - 1993/12/1

Y1 - 1993/12/1

N2 - The reaction of (E)- and (Z)-[W(CO)5(PPhCHPhCHPh)] complexes with [M(PR3)2(C2H4)] [M = Pd, (PR3)2 = dppe (Ph2PCH2CH2PPh2); M = Pt, PR3 = PPh3] has been studied and the following products [which result from insertion of the M(PR3)2 frogment into the phosphirane ring] have been fully characterised by NMR spectroscopy: (2R*,3S*,4S*)-(±)-, (2R*,3S*,4R*)-(±)- and (2R*,3S*,4R*)-(±)-[(dppe) Pd(CHPhCHPhPPh)W(CO)5]; (2S*,3S*,4S*)-(±)-, (2S*3R*4R*)-(±)- and (2S*,3S*,4R*)-(±)-[(Ph3P) 2Pt(CHPhCHPhPPh)W(CO)5]; and trans-(2S*,3S*,4R*)-(±)-[(Ph 3P)(OC)Pt-(CHPhCHPhPPh)W(CO)5]. The crystal and molecular structures of (Z)-[W(CO)5(PPhCHPhCHPh)], (2R*,3S*,4R*)-(±)- and (R*,3S*,4S*)-(±)-[(dppe)Pd(CHPhCHPhPPh)W(CO) 5] have been determined. The configurations of the products are interpreted in terms of a transition state in which a P-C bond is η2-co-ordinated to M(PR3)2 fragment.

AB - The reaction of (E)- and (Z)-[W(CO)5(PPhCHPhCHPh)] complexes with [M(PR3)2(C2H4)] [M = Pd, (PR3)2 = dppe (Ph2PCH2CH2PPh2); M = Pt, PR3 = PPh3] has been studied and the following products [which result from insertion of the M(PR3)2 frogment into the phosphirane ring] have been fully characterised by NMR spectroscopy: (2R*,3S*,4S*)-(±)-, (2R*,3S*,4R*)-(±)- and (2R*,3S*,4R*)-(±)-[(dppe) Pd(CHPhCHPhPPh)W(CO)5]; (2S*,3S*,4S*)-(±)-, (2S*3R*4R*)-(±)- and (2S*,3S*,4R*)-(±)-[(Ph3P) 2Pt(CHPhCHPhPPh)W(CO)5]; and trans-(2S*,3S*,4R*)-(±)-[(Ph 3P)(OC)Pt-(CHPhCHPhPPh)W(CO)5]. The crystal and molecular structures of (Z)-[W(CO)5(PPhCHPhCHPh)], (2R*,3S*,4R*)-(±)- and (R*,3S*,4S*)-(±)-[(dppe)Pd(CHPhCHPhPPh)W(CO) 5] have been determined. The configurations of the products are interpreted in terms of a transition state in which a P-C bond is η2-co-ordinated to M(PR3)2 fragment.

U2 - 10.1039/DT9930001811

DO - 10.1039/DT9930001811

M3 - Article

AN - SCOPUS:37049077267

SN - 0300-9246

SP - 1811

EP - 1822

JO - Journal of the Chemical Society - Dalton Transactions

JF - Journal of the Chemical Society - Dalton Transactions

IS - 12

ER -

An η2 transition state for the insertion of M(PR3)2 fragments (M = Pd or Pt) into the phosphorus-carbon bonds of pentacarbonyl(phosphirane)tungsten complexes

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An η² transition state for the insertion of M(PR₃)₂ fragments (M = Pd or Pt) into the phosphorus-carbon bonds of pentacarbonyl(phosphirane)tungsten complexes