Ruthenium-Capping of Di- and Tetraethynylbiphenyls

Abstract

The di‐ and tetraalkynyl biphenyls 3 and 5 have been synthesized from the tetrabromo derivative 1 by using Pd‐catalyzed cross‐coupling reactions. The reaction of 3 or 5 with cis‐[RuCl2(dppe)2] (8) affords vinylidene ruthenium complexes, which were deprotonated with Et3N to give the terminal σ‐alkynylruthenium derivatives 9−12. The reaction of 3 or 5 with [Ru(CO)ClH(PPh3)3] (13) gave the corresponding di‐σ‐alkenyl ruthenium complexes 14 and 15.

Bridge dominated oxidation of a diruthenium 1,3-divinylphenylene complex

“…4,5 The close resemblance of the divinylphenylene ligand to the repeat units of poly-phenylenevinylenes (PPVs), which constitute one of the most important classes of conducting polymers, 6 provided a further incentive for undertaking such a study. Here we report our findings on the meta-bridged diruthenium complex E,E- 4,7,8 When 1 was subjected to voltammetric studies in CH 2 Cl 2 /NBu 4 PF 6 , two well separated and chemically reversible one-electron waves were detected at +0.235 and +0.555 V as calibrated against the ferrocene/ferrocenium couple. The DE 1/2 of 320 mV signals, at first glance, a fairly strong metal-metal interaction, much stronger than that observed in comparable 1,3-diethynylbenzene bridged diiron complexes (DE 1/2 = 125 mV).…”

Preparation of rhenium hydride complexes with pyrazole and pyrazolato ligands

“…A brown solid slowly separated out from the resulting solution which was filtered and crystallised from CH 2 Cl 2 and ethanol [250 mg, 75% (3a), 245 mg, 73% (3b)]. Found: C,61.60;H,4.38;N,7.03%. C 50 H 42 N 5 OP 2 Re (3a) requires: C,61.46;H,4.33;N,7.17.…”

“…Found: C,61.60;H,4.38;N,7.03%. C 50 H 42 N 5 OP 2 Re (3a) requires: C,61.46;H,4.33;N,7.17. Found: C,61.72;H,4.34;N,7.05%.…”

“…C 50 H 42 N 5 OP 2 Re (3a) requires: C,61.46;H,4.33;N,7.17. Found: C,61.72;H,4.34;N,7.05%. C 51 H 44 N 5 OP 2 Re (3b) requires: C, 61.81; H, 4.47; N, 7.07.…”

A simple synthesis of trans-RuCl(CCR)(dppe)2 complexes and representative molecular structures

“…The chemistry of transition metal complexes transRuCl(C"CR)(dppe) 2 is very well established [1][2][3][4][5][6][7][8][9][10], with a considerable body of recent research demonstrating the utility of these moieties in the construction of multimetallic complexes [11][12][13][14][15], optical materials [16][17][18], including those that exhibit pH or redox-switchable NLO response [19][20][21][22][23][24][25], colormetric [26] and fluorescent [27] sensing behaviour, the ''wire-like" behaviour that arises from extensive d-p mixing along the Ru-C"C fragment [28][29][30][31][32][33][34][35][36][37], and other characteristics that make these compounds potentially useful molecular electronic components [5,33,34,[38][39][40][41]. The facile replacement of the chloride ligand in complexes trans-RuCl(C"CR)(dppe) 2 either directly or from related vinylidenes with a second alkynyl ligand is well documented …”