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Most Requested Journal Articles 3Q04-Chemistry and Related Science

Following is one of the journal articles most requested by researchers using CAS online services.

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CAS indexed 51 chemical substances from this document. CAS subject entries for this document include: Alkynes; Crystal structure; Molecular structure; and 1 additional concept.

CAPLUS COPYRIGHT 2004 ACS on STN

TITLE:	Reactions of the Tetrahedral Clusters [MCo3(CO)12]- (M = Ru, Fe) with Functional Mono- and Diynes
AUTHOR(S):	Choualeb, Aldjia; Braunstein, Pierre; Rose, Jacky; Welter, Richard
CORPORATE SOURCE:	Laboratoire de Chimie de Coordination (UMR 7513 CNRS), Universite Louis Pasteur, Strasbourg, F-67070, Fr.
SOURCE:	Inorganic Chemistry (2004), 43(1), 57-71 CODEN: INOCAJ; ISSN: 0020-1669
PUBLISHER:	American Chemical Society
LANGUAGE:	English

ABSTRACT:
The tetrahedral cluster [RuCo3(CO)12]- reacts with various alkynes, including the new PhC.tplbond.CC(O)NHCH2C.tplbond.CH (L1), to afford the butterfly clusters [RuCo3(CO)10(.mu.4-.eta.2-RC2R')]- (1, R = R' = C(O)OMe; 2, R = H, R' = Ph; 3, R = H, R' = MeC:CH2; 4, R = H, R' = CH2OCH2C.tplbond.CH; 5, R = H, R' = CH2NHC(O)C.tplbond.CPh), in which the ruthenium atom occupies a hinge position and the alkyne is coordinated in a .mu.4-.eta.2 fashion. Reaction of the anions 1-3 with [Cu(NCMe)4]BF4 led to selective loss of the 12e fragment Co(CO)- to form [RuCo2(CO)9(.mu.3-.eta.2-RC2R')] (6, R = R' = C(O)OMe; 7, R = H, R' = Ph; 8, R = H, R' = MeC:CH2). To prep. functionalized RuCo3 or FeCo3 clusters that could be subsequently condensed with a silica matrix via the sol-gel method, [MCo3(CO)12]- (M = Ru, Fe) reacted with the alkyne PhC.tplbond.CC(O)NH(CH2)3Si(OMe)3 (L2) and obtained the butterfly clusters [MCo3(CO)10(.mu.4-.eta.2-PhC2C(O)NH(CH2)3Si(OMe)3)]- 9 and 10, resp. Air-stable [RuCo3(CO)10(.mu.4-.eta.2-Me3SiC2C.tplbond.CSiMe3)]- (11) was obtained from 1,4-bis(trimethylsilyl)butadiyne and reacted with [Cu(NCMe)4]BF4 to give [RuCo2(CO)9(.mu.3-.eta.2-HC2C.tplbond.CSiMe3)] (12), owing to partial ligand proto-desilylation, and not the expected [RuCo2(CO)9(.mu.3-.eta.2-Me3SiC2C.tplbond.CSiMe3)]. Reaction of 11 with [NO]BF4 afforded, in addn. to 12, [RuCo3(CO)9(NO)(.mu.4-.eta.2-Me3SiC2C.tplbond.CSiMe3)] (13) owing to selective CO substitution on a wing-tip cobalt atom with NO. The thermal reaction of 11 with [AuCl(PPh3)] led to replacement of a CO on Ru by the PPh3 originating from [AuCl(PPh3)] and afforded [RuCo3(CO)9(PPh3)(.mu.4-.eta.2-Me3SiC2C.tplbond.CSiMe3)]- (14), also obtained directly by reaction of 11 with one equiv. of PPh3. Proto-desilylation of 11 using TBAF/THF-H2O afforded [RuCo3(CO)10(.mu.4-.eta.2-Me3SiC2C.tplbond.CH)]- (15) which, by Sonogashira coupling with 1,4-diiodobenzene, yielded the dicluster complex [{[RuCo3(CO)10(.mu.4-.eta.2-Me3SiC2C.tplbond.C)]}2C6H4]2- (16). The crystal structures of NEt4.cntdot.3a, NEt4.cntdot.4a, 6, NEt4.cntdot.11b, NEt4.cntdot.14, and [N(n-Bu)4].cntdot.15a have been detd. by x-ray diffraction. Preliminary results indicate the potential of silica-tethered alkyne mixed-metal clusters, obtained by the sol-gel method, as precursors to bimetallic particles.

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