2000
DOI: 10.1021/ar9900109
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What Do Titano- and Zirconocenes Do with Diynes and Polyynes?

Abstract: A thorough investigation of the reactions of diynes, R(C&tbd1;C)(2)R, and polyynes, R(C&tbd1;C)(n)()R, with titanocene and zirconocene was performed using the metallocene sources Cp(2)M(L)(eta(2)-Me(3)SiC&tbd1;CSiMe(3)) (M = Ti, L = -; M = Zr, L = THF, pyridine). The conversions show an array of different products generated in complexation, coupling, and cleavage reactions. These results include remarkable structures (e.g., five-membered metallacyclocumulenes) and reactions (e.g., C-C single-bond cleavage). In… Show more

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Cited by 255 publications
(151 citation statements)
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“…Other advantages of such a synthesis are the transition metal catalysts-free coupling of N-heterocycle with the chloroaminopyridine and easy separation of solid byproducts (ammonium salt of corresponding N-heterocycle) by filtration. Introduction of two amines on the pyridine ring enhances the electron-donating ability of the ligands (Scheme 10) which has also been indicated through crystal structure of complexes (17,20,23), and the sum of angles around nitrogen of N-heterocycle is 353°-360°(for example, the sum of bond angles in complex 20 = 360°, Fig. 5) which reveals sp 2 hybridization of N-atom.…”
Section: Synthesis Of Ti-complexes With Electron-rich Bulky Ligandsmentioning
confidence: 78%
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“…Other advantages of such a synthesis are the transition metal catalysts-free coupling of N-heterocycle with the chloroaminopyridine and easy separation of solid byproducts (ammonium salt of corresponding N-heterocycle) by filtration. Introduction of two amines on the pyridine ring enhances the electron-donating ability of the ligands (Scheme 10) which has also been indicated through crystal structure of complexes (17,20,23), and the sum of angles around nitrogen of N-heterocycle is 353°-360°(for example, the sum of bond angles in complex 20 = 360°, Fig. 5) which reveals sp 2 hybridization of N-atom.…”
Section: Synthesis Of Ti-complexes With Electron-rich Bulky Ligandsmentioning
confidence: 78%
“…Major industrial production of these polymers primarily utilizes group-IV metal catalysts [3][4][5][6]. A revolution was initiated by Zeigler and Natta by the discovery of group-IV metal catalysts due to their enormous industrial application which also inspired intensive research and development of these catalysts for olefin polymerization [4] that ultimately led to the development of group-IV metallocene catalysts for olefins polymerization using Alalkyls as co-catalyst [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26]. Following breakthrough occurred in 1970 with the discovery of Cp 2 TiCl 2 /AlMe 2 Cl and Cp 2 TiMe 2 /AlMe 3 catalysts, but their catalyzing abilities were low.…”
Section: Introductionmentioning
confidence: 99%
“…Some years ago we came to the question of heterobimetallics by investigating the C-C single bond cleavage reactions of 1,3-butadiynes as the basic for their C-C single bond metathesis. We could show that in some cases such a reaction is only possible by combinations like Ti-Ni or Zr-Ni [3,4]. Later we described Ti-Co compounds, obtained by N-N cleavage reaction of 2,3-diazadienes [5].…”
Section: Discussionmentioning
confidence: 96%
“…The activation of several bonds in reactions of different titanocene and zirconocene complexes of bis(trimethylsilyl)acetylene was described in several reviews [1][2][3][4]. For example, cleavage of C-H,C-C,Si-C,N-H,N-C,N-N,N-O,C-O,C-F and C-Bbonds gave complexes of potential applicability in stoichiometrica nd catalyticr eactions.…”
Section: Discussionmentioning
confidence: 99%