Tris(tert-butyl isocyanide-κC)carbonylnickel(0)

Abstract

The title compound, [Ni(C5H9N)3(CO)], was prepared from Ni(CO)4 and a tenfold excess of tert-butyl isocyanide. It crystallizes with two symmetry-independent mol­ecules per asymmetric unit. The central Ni atom of each independent mol­ecule has a nearly perfect tetra­hedral coordination environment, comprising one carbon monoxide and three isocyanide ligands. The title compound is the first structurally characterized Ni0 compound with a mixed CO/RNC coordination.

Detection and Characterization of Mononuclear Pd(I) Complexes Supported by N2S2 and N4 Tetradentate Ligands

“…To the best of our knowledge, there is only one other tBuNC bridged complex that has been reported to date: 46 The bond length of CN of the bridged tBuNC group in 7 is 1.162 Å, slightly longer than the reported bridged C−N bond length (1.141 Å) in the Cu(I) complex but significantly shorter than the average bond distance of a CN double bond (1.279 Å). 47 Given that this C−N bond length it is also comparable to that of the terminal tBuNC ligand in 4 (1.157 Å) and the other reported complexes with terminal tBuNC groups, 48,49 it suggests that the bonding interaction between the tBuNC ligand and the Pd center should not be defined as a "Pd II − (tBuNC − )" system containing a redox noninnocent tBuNC ligand. Therefore, the observed diamagnetism of 7 is likely due to the antiferromagnetic coupling between the two Pd(I) centers, with the bond distance of Pd(I)−Pd(I) (2.7416 Å) comparable to but slightly longer (0.04−0.14 Å) than other reported Pd(I)−Pd(I) bonding interactions.…”

“…The bond length of CN of the bridged tBuNC group in 7 is 1.162 Å, slightly longer than the reported bridged C–N bond length (1.141 Å) in the Cu­(I) complex but significantly shorter than the average bond distance of a CN double bond (1.279 Å) . Given that this C–N bond length it is also comparable to that of the terminal tBuNC ligand in 4 (1.157 Å) and the other reported complexes with terminal tBuNC groups, , it suggests that the bonding interaction between the tBuNC ligand and the Pd center should not be defined as a “Pd II –(tBuNC – )” system containing a redox noninnocent tBuNC ligand. Therefore, the observed diamagnetism of 7 is likely due to the antiferromagnetic coupling between the two Pd­(I) centers, with the bond distance of Pd­(I)–Pd­(I) (2.7416 Å) comparable to but slightly longer (0.04–0.14 Å) than other reported Pd­(I)–Pd­(I) bonding interactions. ,, While the Pd–N ave bond length is comparable to other (κ 2 -N2S2)­Pd II complexes, the Pd–S bond (2.6588 Å) is significantly longer than that in 4 , likely due to the conformation change of N2S2 between 4 in which the two S atoms interact in the equatorial plane, while in 7 one S atom occupies an axial position with an elongated bonding interaction.…”

Insertion vs Ligand Exchange: Reactivity of DistannaAnsaHalf-Sandwich Complexes of Molybdenum and Tungsten toward Isocyanide and Phosphine Complexes of Nickel and Palladium

“…Since the treatment of 3a , b with pure tert -butyl isocyanide or triethylphosphine leads to no reaction, it is assumed that the nickel species plays a decisive role in the observed ligand exchange reaction. This was confirmed by the appearance of the known compound [( t BuNC) 3 Ni(CO)] in the reaction mixture, a single crystal of which could be isolated. The product was identified by comparison of its elemental cell and diffraction data with those reported in the literature.…”