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The Pentynoate Ligand as a Building Block for Multimetallic Systems
Author(s) -
Lin Yvonne H.,
Duclaux Loraine,
Gonzàlez de Rivera Ferran,
Thompson Amber L.,
WiltonEly James D. E. T.
Publication year - 2014
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/ejic.201301504
Subject(s) - chemistry , alkyne , osmium , ligand (biochemistry) , medicinal chemistry , reactivity (psychology) , stereochemistry , yield (engineering) , ruthenium , catalysis , organic chemistry , biochemistry , materials science , receptor , alternative medicine , pathology , metallurgy , medicine
The complexes [RuRCl(CO)(BTD)(PPh 3 ) 2 ] (R = CH=CH t Bu, CH=CHC 6 H 4 Me‐4, CH=CHC 5 H 4 FeC 5 H 5 ; BTD = 2,1,3‐benzothiadiazole) and [Ru{C(C≡CPh)=CHPh}(CO)(PPh 3 ) 2 ] reacted with pentynoic acid to yield the same complex, [RuCl(O 2 CCH 2 CH 2 C≡CH)(CO)(PPh 3 ) 2 ], through cleavage of the vinyl ligand. In contrast, the products [RuR(O 2 CCH 2 CH 2 C≡CH)(CO)(PPh 3 ) 2 ] were formed when NaO 2 CCH 2 CH 2 C≡CH was used. An osmium example, [Os(CH=CHC 6 H 4 Me‐4)(O 2 CCH 2 CH 2 C≡CH)(CO)(PPh 3 ) 2 ], was also prepared from treatment of [Os(CH=CHC 6 H 4 Me‐4)Cl(CO)(BTD)(PPh 3 ) 2 ] with NaO 2 CCH 2 CH 2 C≡CH. Coupling of the pendant alkyne in [RuCl(O 2 CCH 2 CH 2 C≡CH)(CO)(PPh 3 ) 2 ] to yield the homodimetallic complex [{RuCl(O 2 CCH 2 CH 2 C≡C)(CO)(PPh 3 ) 2 } 2 ] was achieved by using [PdCl 2 (PPh 3 ) 2 ], CuI and NEt 3 . The reactivity of the alkyne unit was further exploited by the metallation of the alkyne with ClAu(PR 3 ) (R = Ph, Cy) and Co 2 (CO) 8 to yield the multimetallic species [Ru(CH=CHC 6 H 4 Me‐4)(O 2 CCH 2 CH 2 C≡CAuPR 3 )(CO)(PPh 3 ) 2 ] and [Ru(CH=CHC 6 H 4 Me‐4)(O 2 CCH 2 CH 2 CC{Co 2 (CO) 6 }H)(CO)(PPh 3 ) 2 ]. The structures of the complexes [Ru(CH=CHC 6 H 4 Me‐4)(O 2 CCH 2 CH 2 C≡CH)(CO)(PPh 3 ) 2 ] and [Ru(CH=CH t Bu)(O 2 CCH 2 CH 2 C≡CH)(CO)(PPh 3 ) 2 ] were determined crystallographically.