Synthesis and reactions of terminal osmium and ruthenium complexed phosphinidenes [(η6-Ar)(L)M=PMes*]

Arjan T. Termaten; Tom Nijbacker; Marius Schakel; Martin Lutz; Anthony L. Spek; Koop Lammertsma

doi:10.1002/chem.200204582

Synthesis and reactions of terminal osmium and ruthenium complexed phosphinidenes [(η⁶-Ar)(L)M=PMes*]

Arjan T. Termaten, Tom Nijbacker, Marius Schakel, Martin Lutz, Anthony L. Spek, Koop Lammertsma

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

65 Citations (Scopus)

Abstract

Novel, very stable ruthenium and osmium containing terminal phosphinidene complexes [(η⁶-Ar)-(L)M=PMes*] (Ar=benzene, p-cymene; L = PR₃, CO, and RNC) have been prepared by dehydrohalogenation of novel [(η⁶-Ar)MX₂(PH₂Mes*)] complexes in the presence of a stabilizing ligand. X-ray crystal structures are reported for [(η⁶-C₆H₆)(PPh₃)Ru= PMes*] (9) and [(η⁶-pCy)(PPh₃)Os=PMes*] (4). Dehydrohalogenation in the absence of a stabilizing ligand resulted in the new P-spiroannulated Ru₂P₂-ring structure 16. Dehydrohalogenation in the presence of but-2-yne gave a novel phosphaallyl complex [(η⁶-Ar)Ru(η³-R₂PC- (Me)CHMe)] 26, for which an X-ray crystal structure is reported. The mechanism by which 16 and 26 are obtained is presumed to involve the intermediate formation of the 16-electron (η⁶-benzene)Ru=PMes* phosphinidene complex.

Original language	English
Pages (from-to)	2200-2208
Number of pages	9
Journal	Chemistry - A European Journal
Volume	9
Issue number	10
DOIs	https://doi.org/10.1002/chem.200204582
Publication status	Published - 23 May 2003
Externally published	Yes

Keywords

Heterocycles
Metallacycles
Osmium
P ligands
Phosphorus
Ruthenium

ASJC Scopus subject areas

Catalysis
Organic Chemistry

Access to Document

10.1002/chem.200204582

Cite this

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title = "Synthesis and reactions of terminal osmium and ruthenium complexed phosphinidenes [(η6-Ar)(L)M=PMes*]",

abstract = "Novel, very stable ruthenium and osmium containing terminal phosphinidene complexes [(η6-Ar)-(L)M=PMes*] (Ar=benzene, p-cymene; L = PR3, CO, and RNC) have been prepared by dehydrohalogenation of novel [(η6-Ar)MX2(PH2Mes*)] complexes in the presence of a stabilizing ligand. X-ray crystal structures are reported for [(η6-C6H6)(PPh3)Ru= PMes*] (9) and [(η6-pCy)(PPh3)Os=PMes*] (4). Dehydrohalogenation in the absence of a stabilizing ligand resulted in the new P-spiroannulated Ru2P2-ring structure 16. Dehydrohalogenation in the presence of but-2-yne gave a novel phosphaallyl complex [(η6-Ar)Ru(η3-R2PC- (Me)CHMe)] 26, for which an X-ray crystal structure is reported. The mechanism by which 16 and 26 are obtained is presumed to involve the intermediate formation of the 16-electron (η6-benzene)Ru=PMes* phosphinidene complex.",

keywords = "Heterocycles, Metallacycles, Osmium, P ligands, Phosphorus, Ruthenium",

author = "Termaten, {Arjan T.} and Tom Nijbacker and Marius Schakel and Martin Lutz and Spek, {Anthony L.} and Koop Lammertsma",

year = "2003",

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doi = "10.1002/chem.200204582",

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T1 - Synthesis and reactions of terminal osmium and ruthenium complexed phosphinidenes [(η6-Ar)(L)M=PMes*]

AU - Termaten, Arjan T.

AU - Nijbacker, Tom

AU - Schakel, Marius

AU - Lutz, Martin

AU - Spek, Anthony L.

AU - Lammertsma, Koop

PY - 2003/5/23

Y1 - 2003/5/23

N2 - Novel, very stable ruthenium and osmium containing terminal phosphinidene complexes [(η6-Ar)-(L)M=PMes*] (Ar=benzene, p-cymene; L = PR3, CO, and RNC) have been prepared by dehydrohalogenation of novel [(η6-Ar)MX2(PH2Mes*)] complexes in the presence of a stabilizing ligand. X-ray crystal structures are reported for [(η6-C6H6)(PPh3)Ru= PMes*] (9) and [(η6-pCy)(PPh3)Os=PMes*] (4). Dehydrohalogenation in the absence of a stabilizing ligand resulted in the new P-spiroannulated Ru2P2-ring structure 16. Dehydrohalogenation in the presence of but-2-yne gave a novel phosphaallyl complex [(η6-Ar)Ru(η3-R2PC- (Me)CHMe)] 26, for which an X-ray crystal structure is reported. The mechanism by which 16 and 26 are obtained is presumed to involve the intermediate formation of the 16-electron (η6-benzene)Ru=PMes* phosphinidene complex.

AB - Novel, very stable ruthenium and osmium containing terminal phosphinidene complexes [(η6-Ar)-(L)M=PMes*] (Ar=benzene, p-cymene; L = PR3, CO, and RNC) have been prepared by dehydrohalogenation of novel [(η6-Ar)MX2(PH2Mes*)] complexes in the presence of a stabilizing ligand. X-ray crystal structures are reported for [(η6-C6H6)(PPh3)Ru= PMes*] (9) and [(η6-pCy)(PPh3)Os=PMes*] (4). Dehydrohalogenation in the absence of a stabilizing ligand resulted in the new P-spiroannulated Ru2P2-ring structure 16. Dehydrohalogenation in the presence of but-2-yne gave a novel phosphaallyl complex [(η6-Ar)Ru(η3-R2PC- (Me)CHMe)] 26, for which an X-ray crystal structure is reported. The mechanism by which 16 and 26 are obtained is presumed to involve the intermediate formation of the 16-electron (η6-benzene)Ru=PMes* phosphinidene complex.

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KW - Metallacycles

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KW - P ligands

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