The first co-ordinatively unsaturated group 8 allenylidene complexes: Insights into Grubbs' vs. Dixneuf-Fürstner olefin metathesis catalysts

Karsten J. Harlow; Anthony F. Hill; James D.E.T. Wilton-Ely

doi:10.1039/a808817i

The first co-ordinatively unsaturated group 8 allenylidene complexes: Insights into Grubbs' vs. Dixneuf-Fürstner olefin metathesis catalysts

Karsten J. Harlow, Anthony F. Hill^*, James D.E.T. Wilton-Ely

^*Corresponding author for this work

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

155 Citations (Scopus)

Abstract

The reactions of [MCl₂(PPh₃)₃] with HC≡CCPh₂OH provided [MCl₂(=C=C=CPh₂)(PPh₃)₂] (M = Ru 1a or Os 1b) the first examples of co-ordinatively unsaturated allenylidene complexes of Group 8 metals. The phosphine ligands of 1a are labile and readily replaced by PCy₃ to give [RuCl₂(=C=C=CPh₂)(PCy₃)₂] 1c. Heating 1a with NaPF₆ in chloroform gave the known bimetallic salt [Ru₂(μ-Cl)₃(=C=C=CPh₂)₂(PPh ₃)₄]PF₆ 2·PF₆. The reaction of 1a with carbon monoxide provided [RuCl₂(=C=C=Ph₂)(CO)(PPh₃)₂] 3 which may also be prepared from [RuCl₂(CO)(dmf)(PPh₃)₂] and HC≡CCPh₂OH. The first macrocycle coligated allenylidene complex [RuCl(=C=C=CPh₂)(PPh₃)([9]aneS₃)]Cl 4·Cl ([9]aneS₃ = 1,4,7-trithiacyclononane) was obtained from the reaction of 1a with [9]aneS₃. Alternatively, 4·PF₆ is also obtained by treating [RuCl₂(PPh₃)([9]aneS₃)] sequentially with NaPF₆ in acetonitrile followed by HC≡CCPh₂OH. The reaction of 1a with dppe and NaPF₆ yielded the known salt trans-[RuCl(=C=C=CPh₂)(dppe)₂]PF₆ 5·PF₆. The complex [RuCl(=C=C=CPh₂)(PCy₃){HB(pz)₃}] 6 (pz = pyrazol-1-yl) was obtained from the reaction of 1c with K[HB(pz)₃], whilst the related benzylidene complex [RuCl(=CHPh)(PCy₃){HB(pz)₃}] 7 was obtained similarly from [RuCl₂(=CHPh)(PCy₃)₂] and K[HB(pz)₃]. Heating [Ru₂(μ-Cl)₂Cl₂(η-cym)₂] (cym = ¹PrC₆H₄Me-4) with PCy₃ and HC≡CCPh₂OH in refluxing benzene provided a mixture of 1c and the bimetallic complex [Ru₂(μ-Cl₂)Cl₂(=C=C=CPh ₂)-(η-cym)] 8 and other unidentified products. The complex 8 may however be obtained quantitatively from the reaction of 1c with [Ru₂(μ-Cl)₂Cl₂(η-cym)₂]. These results suggest that the active species in ring-closure olefin metathesis processes mediated by the allenylidene pre-catalyst [RuCl(=C=C=CPh₂)(PCy₃)(η-cym)]⁺ in non-polar arene solvents may be allenylidene analogues of the Grubbs' alkene metathesis catalyst, viz. 1c and 8.

Original language	English
Pages (from-to)	285-291
Number of pages	7
Journal	Journal of the Chemical Society. Dalton Transactions
Issue number	3
DOIs	https://doi.org/10.1039/a808817i
Publication status	Published - 7 Feb 1999
Externally published	Yes

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@article{046f2dfe48454b538af893e16bd359a9,

title = "The first co-ordinatively unsaturated group 8 allenylidene complexes: Insights into Grubbs' vs. Dixneuf-F{\"u}rstner olefin metathesis catalysts",

abstract = "The reactions of [MCl2(PPh3)3] with HC≡CCPh2OH provided [MCl2(=C=C=CPh2)(PPh3)2] (M = Ru 1a or Os 1b) the first examples of co-ordinatively unsaturated allenylidene complexes of Group 8 metals. The phosphine ligands of 1a are labile and readily replaced by PCy3 to give [RuCl2(=C=C=CPh2)(PCy3)2] 1c. Heating 1a with NaPF6 in chloroform gave the known bimetallic salt [Ru2(μ-Cl)3(=C=C=CPh2)2(PPh 3)4]PF6 2·PF6. The reaction of 1a with carbon monoxide provided [RuCl2(=C=C=Ph2)(CO)(PPh3)2] 3 which may also be prepared from [RuCl2(CO)(dmf)(PPh3)2] and HC≡CCPh2OH. The first macrocycle coligated allenylidene complex [RuCl(=C=C=CPh2)(PPh3)([9]aneS3)]Cl 4·Cl ([9]aneS3 = 1,4,7-trithiacyclononane) was obtained from the reaction of 1a with [9]aneS3. Alternatively, 4·PF6 is also obtained by treating [RuCl2(PPh3)([9]aneS3)] sequentially with NaPF6 in acetonitrile followed by HC≡CCPh2OH. The reaction of 1a with dppe and NaPF6 yielded the known salt trans-[RuCl(=C=C=CPh2)(dppe)2]PF6 5·PF6. The complex [RuCl(=C=C=CPh2)(PCy3){HB(pz)3}] 6 (pz = pyrazol-1-yl) was obtained from the reaction of 1c with K[HB(pz)3], whilst the related benzylidene complex [RuCl(=CHPh)(PCy3){HB(pz)3}] 7 was obtained similarly from [RuCl2(=CHPh)(PCy3)2] and K[HB(pz)3]. Heating [Ru2(μ-Cl)2Cl2(η-cym)2] (cym = 1PrC6H4Me-4) with PCy3 and HC≡CCPh2OH in refluxing benzene provided a mixture of 1c and the bimetallic complex [Ru2(μ-Cl2)Cl2(=C=C=CPh 2)-(η-cym)] 8 and other unidentified products. The complex 8 may however be obtained quantitatively from the reaction of 1c with [Ru2(μ-Cl)2Cl2(η-cym)2]. These results suggest that the active species in ring-closure olefin metathesis processes mediated by the allenylidene pre-catalyst [RuCl(=C=C=CPh2)(PCy3)(η-cym)]+ in non-polar arene solvents may be allenylidene analogues of the Grubbs' alkene metathesis catalyst, viz. 1c and 8.",

keywords = "Organometallic macrocycle chemistry, Ray crystal-structure, 1,4,7-trithiacyclononane, 1,4,8,11-tetrathiacyclotetradecane, Rearrangement, Rucl2(pph3)3, Dimerization, Mechanism",

author = "Harlow, {Karsten J.} and Hill, {Anthony F.} and Wilton-Ely, {James D.E.T.}",

year = "1999",

month = feb,

day = "7",

doi = "10.1039/a808817i",

language = "English",

pages = "285--291",

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

issn = "1470-479X",

publisher = "Royal Society of Chemistry",

number = "3",

}

TY - JOUR

T1 - The first co-ordinatively unsaturated group 8 allenylidene complexes

T2 - Insights into Grubbs' vs. Dixneuf-Fürstner olefin metathesis catalysts

AU - Harlow, Karsten J.

AU - Hill, Anthony F.

AU - Wilton-Ely, James D.E.T.

PY - 1999/2/7

Y1 - 1999/2/7

N2 - The reactions of [MCl2(PPh3)3] with HC≡CCPh2OH provided [MCl2(=C=C=CPh2)(PPh3)2] (M = Ru 1a or Os 1b) the first examples of co-ordinatively unsaturated allenylidene complexes of Group 8 metals. The phosphine ligands of 1a are labile and readily replaced by PCy3 to give [RuCl2(=C=C=CPh2)(PCy3)2] 1c. Heating 1a with NaPF6 in chloroform gave the known bimetallic salt [Ru2(μ-Cl)3(=C=C=CPh2)2(PPh 3)4]PF6 2·PF6. The reaction of 1a with carbon monoxide provided [RuCl2(=C=C=Ph2)(CO)(PPh3)2] 3 which may also be prepared from [RuCl2(CO)(dmf)(PPh3)2] and HC≡CCPh2OH. The first macrocycle coligated allenylidene complex [RuCl(=C=C=CPh2)(PPh3)([9]aneS3)]Cl 4·Cl ([9]aneS3 = 1,4,7-trithiacyclononane) was obtained from the reaction of 1a with [9]aneS3. Alternatively, 4·PF6 is also obtained by treating [RuCl2(PPh3)([9]aneS3)] sequentially with NaPF6 in acetonitrile followed by HC≡CCPh2OH. The reaction of 1a with dppe and NaPF6 yielded the known salt trans-[RuCl(=C=C=CPh2)(dppe)2]PF6 5·PF6. The complex [RuCl(=C=C=CPh2)(PCy3){HB(pz)3}] 6 (pz = pyrazol-1-yl) was obtained from the reaction of 1c with K[HB(pz)3], whilst the related benzylidene complex [RuCl(=CHPh)(PCy3){HB(pz)3}] 7 was obtained similarly from [RuCl2(=CHPh)(PCy3)2] and K[HB(pz)3]. Heating [Ru2(μ-Cl)2Cl2(η-cym)2] (cym = 1PrC6H4Me-4) with PCy3 and HC≡CCPh2OH in refluxing benzene provided a mixture of 1c and the bimetallic complex [Ru2(μ-Cl2)Cl2(=C=C=CPh 2)-(η-cym)] 8 and other unidentified products. The complex 8 may however be obtained quantitatively from the reaction of 1c with [Ru2(μ-Cl)2Cl2(η-cym)2]. These results suggest that the active species in ring-closure olefin metathesis processes mediated by the allenylidene pre-catalyst [RuCl(=C=C=CPh2)(PCy3)(η-cym)]+ in non-polar arene solvents may be allenylidene analogues of the Grubbs' alkene metathesis catalyst, viz. 1c and 8.

AB - The reactions of [MCl2(PPh3)3] with HC≡CCPh2OH provided [MCl2(=C=C=CPh2)(PPh3)2] (M = Ru 1a or Os 1b) the first examples of co-ordinatively unsaturated allenylidene complexes of Group 8 metals. The phosphine ligands of 1a are labile and readily replaced by PCy3 to give [RuCl2(=C=C=CPh2)(PCy3)2] 1c. Heating 1a with NaPF6 in chloroform gave the known bimetallic salt [Ru2(μ-Cl)3(=C=C=CPh2)2(PPh 3)4]PF6 2·PF6. The reaction of 1a with carbon monoxide provided [RuCl2(=C=C=Ph2)(CO)(PPh3)2] 3 which may also be prepared from [RuCl2(CO)(dmf)(PPh3)2] and HC≡CCPh2OH. The first macrocycle coligated allenylidene complex [RuCl(=C=C=CPh2)(PPh3)([9]aneS3)]Cl 4·Cl ([9]aneS3 = 1,4,7-trithiacyclononane) was obtained from the reaction of 1a with [9]aneS3. Alternatively, 4·PF6 is also obtained by treating [RuCl2(PPh3)([9]aneS3)] sequentially with NaPF6 in acetonitrile followed by HC≡CCPh2OH. The reaction of 1a with dppe and NaPF6 yielded the known salt trans-[RuCl(=C=C=CPh2)(dppe)2]PF6 5·PF6. The complex [RuCl(=C=C=CPh2)(PCy3){HB(pz)3}] 6 (pz = pyrazol-1-yl) was obtained from the reaction of 1c with K[HB(pz)3], whilst the related benzylidene complex [RuCl(=CHPh)(PCy3){HB(pz)3}] 7 was obtained similarly from [RuCl2(=CHPh)(PCy3)2] and K[HB(pz)3]. Heating [Ru2(μ-Cl)2Cl2(η-cym)2] (cym = 1PrC6H4Me-4) with PCy3 and HC≡CCPh2OH in refluxing benzene provided a mixture of 1c and the bimetallic complex [Ru2(μ-Cl2)Cl2(=C=C=CPh 2)-(η-cym)] 8 and other unidentified products. The complex 8 may however be obtained quantitatively from the reaction of 1c with [Ru2(μ-Cl)2Cl2(η-cym)2]. These results suggest that the active species in ring-closure olefin metathesis processes mediated by the allenylidene pre-catalyst [RuCl(=C=C=CPh2)(PCy3)(η-cym)]+ in non-polar arene solvents may be allenylidene analogues of the Grubbs' alkene metathesis catalyst, viz. 1c and 8.

KW - Organometallic macrocycle chemistry

KW - Ray crystal-structure

KW - 1,4,7-trithiacyclononane

KW - 1,4,8,11-tetrathiacyclotetradecane

KW - Rearrangement

KW - Rucl2(pph3)3

KW - Dimerization

KW - Mechanism

UR - http://www.scopus.com/inward/record.url?scp=33750595439&partnerID=8YFLogxK

U2 - 10.1039/a808817i

DO - 10.1039/a808817i

M3 - Article

SN - 1470-479X

SP - 285

EP - 291

JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

IS - 3

ER -

The first co-ordinatively unsaturated group 8 allenylidene complexes: Insights into Grubbs' vs. Dixneuf-Fürstner olefin metathesis catalysts

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