Transition metal-cyanocarbon chemistry

The First Cyclopentadienylalkylphosphane Nickel Chelates: Synthesis, Structures, and Reactions

“…[59,60] In most cases, the cyclobutenylmetal complexes obtained by [2 + 2] cycloaddition rapidly undergo electrocyclic ring opening. [59][60][61][62][63][64][65][66][67] Nickel acetylide chelates 14 and 15 were treated with an excess of TCNE over 14 h to afford cross-conjugated dienylnickel chelates 23 and 24 as dark-brown solids in 80 and 79 % yield, respectively. [59][60][61][62][63][64][65][66][67] Nickel acetylide chelates 14 and 15 were treated with an excess of TCNE over 14 h to afford cross-conjugated dienylnickel chelates 23 and 24 as dark-brown solids in 80 and 79 % yield, respectively.…”

Cyanoacetylenes and cyanoacetylides: versatile ligands in organometallic chemistry

“…The reaction of 2 with [Co 2 (CO) 6 (dppm)] resulted in the formation of a dark red solution from which only 4 could be isolated. However, when 4 was allowed to react with [RuCl-(PPh 3 ) 2 Cp] in the presence of NH 4 PF 6 , a bright red solution was obtained, from which [Co 2 (µ-η 2 -PhC 2 C᎐ ᎐ ᎐ N{Ru(PPh 3 ) 2 -Cp})(CO) 4 (dppm)]PF 6 (5) was isolated as a brick-red powder (Scheme 1). The composition of the complex was established spectroscopically while careful recrystallisation at low temperature afforded red cube-shaped crystals of 5.…”

“…The reaction of 2 with [Co 2 (CO) 6 (dppm)] resulted in the formation of a dark red solution from which only 4 could be isolated. However, when 4 was allowed to react with [RuCl-(PPh 3 ) 2 Cp] in the presence of NH 4 PF 6 , a bright red solution was obtained, from which [Co 2 (µ-η 2 -PhC 2 C᎐ ᎐ ᎐ N{Ru(PPh 3 ) 2 -Cp})(CO) 4 (dppm)]PF 6(5) was isolated as a brick-red powder (Scheme 1). The composition of the complex was established spectroscopically while careful recrystallisation at low temperature afforded red cube-shaped crystals of 5.The 1 H and 13 C NMR spectra of 5 clearly indicated the formation of the heterometallic species, with sharp singlets at δ 4.30 ( 1 H) and 84.34 ( 13 C) together with unresolved multiplet resonances centred at 3.28 ( 1 H), and 35.84 ( 13 C) confirming the presence of both Cp and dppm ligands.…”

Reactions of bis(diphenylphosphine)acetylene with metal carbonyl complexes

“…The less positive value for the P(acetylide) ( 23.00) found for 2b, in comparison to 2a, and the absence of a 2 J PP coupling constant suggest that the P(acetylide) is not bonded through Co (2). The positive chemical shift P(acetylide) observed for 2b can be understood as resulting from the interaction between CC and the cobalt atom.…”

“…Our interest in alkyne chemistry [1][2][3][4][5][6][7] prompted us to investigate the behavior of bis(diphenylphosphine)acetylene, (DPPA), towards some metal-carbonyl complexes. DPPA is a potentially tridentate ligand, whose coordination capability has been extensively studied [8][9][10][11].…”