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2‐Oxacyclopentylidene, 2‐Oxacyclohexylidene, and 2‐Oxacycloheptylidene Rhenium Complexes by Reaction of ω‐Alkynols with the [{MeC(CH 2 PPh 2 ) 3 }Re(CO) 2 ] + Auxiliary
Author(s) -
Bianchini Claudio,
Marchi Andrea,
Mantovani Nicoletta,
Marvelli Lorenza,
Masi Dante,
Peruzzini Maurizio,
Rossi Roberto
Publication year - 1998
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199802)1998:2<211::aid-ejic211>3.0.co;2-k
Subject(s) - triphos , chemistry , rhenium , tetrafluoroborate , ligand (biochemistry) , stereochemistry , octahedron , molecule , alkyl , medicinal chemistry , crystallography , crystal structure , organic chemistry , ionic liquid , catalysis , receptor , biochemistry
Various β‐, γ‐, and δ‐alkynols have been reacted with the 16e − fragment [(triphos)Re(CO) 2 ] + generated in situ by H 2 elimination from [(triphos)Re(CO) 2 (η 2 ‐H 2 )]BF 4 [triphos = MeC(CH 2 PPh 2 ) 3 ]. Irrespective of the length of the alkyl chain between the C≡C and OH functional groups in the ω‐alkynol, 2‐oxacyclocarbene complexes are obtained. These include the 2‐oxacyclopentylidene derivatives [(triphos)Re(CO) 2 {=CCH 2 CH 2 CH 2 O}]BF 4 and [(triphos)Re(CO) 2 {=CCH 2 CH 2 CH(Me)O}]BF 4 , the 2‐oxacyclohexylidene dervivatives [(triphos)Re(CO) 2 {=CCH 2 CH 2 CH 2 CH 2 O}]BF 4 and[(triphos)Re(CO) 2 {=CCH 2 CH 2 CH 2 CH(Me)O}]BF 4 , and the 2‐oxacycloheptylidene complex [(triphos)Re(CO) 2 {=CCH 2 CH 2 ‐ CH 2 CH 2 CH 2 O}]BF 4 . The latter compound contains a unprecedented seven‐membered oxacarbene ring. The rhenium‐assisted δ‐alkynol to 2‐oxacyloheptylidene rearrangement proceeds via the hydroxybutylvinylidene kinetic intermediate [(triphos)Re(CO) 2 {C=C(H)CH 2 CH 2 CH 2 CH 2 OH}]BF 4 , which has been characterized in both the solid state and solution. An X‐ray analysis has been carried out on a single crystal of [(triphos)Re(CO) 2 {=CCH 2 CH 2 CH(Me)O}]BF 4 . The structure of this complex consists of [(triphos)Re(CO) 2 {=CCH 2 CH 2 CH(Me)O}] + cations and tetrafluoroborate anions with no interspersed solvent molecules. A facial triphos ligand, two cis ‐disposed carbonyl groups and a 2‐oxacyclopentylidene ligand coordinate the Re centre in a slightly distorted octahedral environment.