Early-late Heterobimetallic Complexes Research Articles

The first chiral early-late heterobimetallic complex — A titanium(IV)-palladium(II) complex based on salenophos

The synthesis of the chiral polyfunctional diphosphine salenophos 1 is described. The new ligand bearing hard and soft coordination sites chelates titanium(IV) as well as palladium(II) in a defined manner provided a certain order during the introduction of the two metals was kept. In this way the first chiral early-late heterobimetallic complex could be synthesized. It was fully characterized by NMR spectroscopy and X-ray structural analysis. Remarkable features of the heterobimetallic complex are the trans coordination of the phosphine groups on palladium and the distance between Ti and Pd which is more than 4.13 Å.

Studies of the reactivity towards insertion and electrophilic processes of Nb-H and Nb(η 2-CS 2) moieties of bis(trimethylsilylcyclopentadienyl)niobium complexes

The interaction of MeI with the complexes [Nb(η 5-C 5H 4SiMe 3)XCS 2-C,S] (X = Cl 1, X = Br 2) affords the cationic complexes containing a methyldithiocarboxylate group, [Nb(η 5-C 5H 4SiMe 3) 2XC(S)SMe-C,S)]I (X = Cl 3, X = Br 4) as the result of the electrophilic attack of MeI in the sulfur ( exo) atom of the coordinated CS 2. In contrast, the trihydride [Nb(η 5-C 5H 4SiMe 3) 2H 3] 5 interact under mild conditions in THF, with phosphites giving rise to new hydrideniobium(III) complexes, [Nb(η 5-C 5H 4SiMe 3) 2HL] (L = P(OMe) 3 6, P(OEt) 3, 7, P(OPh) 3 8). Complexes Nb(η 5-C 5H 4 SiMe 3) 2HL undergo an insertion of CS 2 into the niobium-hydrogen bond to give products, the nature of which are highly dependent on L. With L = CO [Nb(η 5-C 5H 4SiMe 3) 2S(S)CHS)(CO)] 10 is obtained, whereas [Nb(η 5-C 5H 4SiMe 3) 2(SCHSSS)] 11 with an η 2-dithioformate is the product of similar reactions for 6, 7 and 8. Finally, using several electrophile synthons of Group 11 metals, we have prepared two families of early-late heterobimetallic complexes. Compound 1 reacts, through the sulfur ( exo) atom of the CS 2, with [MPPh 3]PF 6 to give cationic heterobimetallic complexes [Nb(η 5-C 5H 4SiMe 3) 2Cl(μ-CS 2)(C(S)SM(PPh 3))][PF 6] (M = CU 12, M = Ag 13, M = Au 14). In a similar way, 6-8 react with [AuPPh 3][PF 6] to give the species containing a hydride bridge [Nb(η 5-C 5H 4SiMe 3) 2L(μ-H)(AuPPh3)][PF 6] (L = P(OMe) 3 15, L = P(OEt) 3 16, L = P(OPh) 3 17). All the complexes described have been characterized using IR and NMR techniques.

Mechanistic Investigations of Cp-Loss Reactions in an Early-Late Heterobimetallic Complex. Isolation of a Cationic Tantalum-Palladium Compound with a Free Cyclopentadienyl Counteranion

Mechanistic Investigations of Cp-Loss Reactions in an Early-Late Heterobimetallic Complex. Isolation of a Cationic Tantalum-Palladium Compound with a Free Cyclopentadienyl Counteranion

Reactivity of an early-late heterobimetallic complex toward phosphines: synthesis, structure, and reactivity of a cationic tantalum-palladium compound with a free cyclopentadienyl counteranion

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTReactivity of an early-late heterobimetallic complex toward phosphines: synthesis, structure, and reactivity of a cationic tantalum-palladium compound with a free cyclopentadienyl counteranionMatthew D. Butts and Robert G. BergmanCite this: Organometallics 1993, 12, 11, 4269–4271Publication Date (Print):November 1, 1993Publication History Published online1 May 2002Published inissue 1 November 1993https://doi.org/10.1021/om00035a005RIGHTS & PERMISSIONSArticle Views142Altmetric-Citations14LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (365 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Synthesis of an early-late heterobimetallic imido complex: cooperative reactivity with nitrogen-, oxygen-, and sulfur-hydrogen bonds and formation of a novel aminophosphine complex

Synthesis of an early-late heterobimetallic imido complex: cooperative reactivity with nitrogen-, oxygen-, and sulfur-hydrogen bonds and formation of a novel aminophosphine complex

Carbonylation of ethene to acrolein in the presence of the early-late heterobimetallic complex [AsPh4][(.eta.5-C5Me5)2Zr(.mu.-S)2Rh(CO)2].cntdot.THF

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCarbonylation of ethene to acrolein in the presence of the early-late heterobimetallic complex [AsPh4][(.eta.5-C5Me5)2Zr(.mu.-S)2Rh(CO)2].cntdot.THFPhilippe Kalck, Carole Serra, Corinne Machet, Roland Broussier, Bernard Gautheron, Genevieve Delmas, Gwenaelle Trouve, and Marek KubickiCite this: Organometallics 1993, 12, 4, 1021–1022Publication Date (Print):April 1, 1993Publication History Published online1 May 2002Published inissue 1 April 1993https://doi.org/10.1021/om00028a014RIGHTS & PERMISSIONSArticle Views154Altmetric-Citations33LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (307 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Synthesis and reactivity of Cp2Ta(CH2)2Ir(CO)2: an early-late heterobimetallic complex that catalytically hydrogenates, isomerizes and hydrosilates alkenes

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and reactivity of Cp2Ta(CH2)2Ir(CO)2: an early-late heterobimetallic complex that catalytically hydrogenates, isomerizes and hydrosilates alkenesMichael J. Hostetler and Robert G. BergmanCite this: J. Am. Chem. Soc. 1990, 112, 23, 8621–8623Publication Date (Print):November 1, 1990Publication History Published online1 May 2002Published inissue 1 November 1990https://doi.org/10.1021/ja00179a078RIGHTS & PERMISSIONSArticle Views455Altmetric-Citations79LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (409 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

A new route to early-late heterobimetallic μ-alkylidene complexes

The reaction of two equivalents of Cp 2ZrHCl ( 1) with Cp(CO) 2ReCHR ( 2, R = CH 2CH 2CMe 3; 4, R = CH 3) led to the formation of the heterobimetallic μ-alkylidene complexes Cp 2Zr(μ-CHR)(μ,η 1,η 2-CO)Re(CO)Cp ( 3, R = CH 2CH 2CMe 3; 5, R = CH 3).