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Reactions of Ethyne with Some Ruthenium Cluster Complexes Containing dppm
Author(s) -
Bruce Michael I.,
Pyke Simon M.,
Zaitseva Natasha N.,
Skelton Brian W.,
White Allan H.
Publication year - 2001
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/1522-2675(20011017)84:10<3197::aid-hlca3197>3.0.co;2-s
Subject(s) - chemistry , ruthenium , ligand (biochemistry) , alkyne , cluster (spacecraft) , crystal structure , thermal decomposition , molecule , stereochemistry , cluster chemistry , chelation , crystallography , medicinal chemistry , catalysis , inorganic chemistry , organic chemistry , biochemistry , receptor , computer science , programming language
Reactions of ethyne with [Ru 3 ( μ ‐dppm)(CO) 10 ] have given isomeric complexes [Ru 3 ( μ 3 ‐C 6 H 6 )(CO) 6 (dppm)], one of which, 2 , contains the dppm chelating an Ru‐atom, together with a hexatrienetriyl ligand attached to the Ru 3 cluster to form a methylideneruthenacyclohexadiene system. The second isomer 3 contains the dppm bridging an Ru−Ru bond, with the C 6 H 6 ligand forming a vinylruthenacyclopentadiene system. Also isolated was the open‐chain Ru 3 complex 4 containing a ruthenacyclopentadiene attached to the central Ru‐atom; the other Ru−Ru vector is bridged by a PPh 2 CHPPh 2 C 4 H 5 ligand, formed by a novel insertion of two ethyne molecules into an Ru−P bond. The reaction of ethyne with [Ru 3 ( μ ‐H)( μ 3 ‐C 2 H 2 )(CO) 9 ] proceeded by attack at the coordinated alkyne and at the cluster to give a cluster‐bonded PPh 2 CH 2 PPh 2 CCH system in 7 . Thermolysis of [Ru 3 ( μ ‐H)( μ 3 ‐C 2 SiMe 3 )( μ ‐dppm)(CO) 7 ] ( 8 ; refluxing MeOH) in the presence of KF gave [Ru 6 ( μ ‐CCH 2 ) 2 ( μ ‐dppm) 2 (CO) 12 ] ( 9 ; 80%); similar reactions carried out with [RuClCp(PPh 3 ) 2 ] also present gave 9 (67%) together with [Ru 3 ( μ ‐H)( μ 3 ‐C 2 H)( μ ‐dppm)(CO) 6 (PPh 3 )] ( 11 ; 23%). The molecular structures of 2 , 3 , 4 , 7 , 9 , and 11 , some as differently solvated forms, have been determined by single‐crystal X‐ray studies.