Synthesis and Structures of Dinuclear Nickel(I) Di-tert-butylarsenido Complexes: X-ray Crystal Structures of [Ni(µ-t-Bu2As)(PMe3)]2(Ni–Ni) and [Ni(µ-t-Bu2As)(CN-p-tol)2]2 (Ni–Ni) (tol = Tolyl)

Richard A. Jones, Bruce R. Whittlesey

Research output: Contribution to journalArticlepeer-review

25 Scopus citations

Abstract

The reaction of NiCl2(PMe3)2 with Li-t-Bu2As in THF at –78 °C gives [Ni(μ-t-Bu2As)PMe3]2 (1) in 37% yield. 1 reacts with excess p-tolyl isocyanide (CN-p-tol) in hexane at room temperature to give [Ni(µ-t-Bu2As)(CN-p-tol)2]2 (2) in 47% yield. 1 and 2 are the First dinickel diorganoarsenido complexes to be structurally characterized by X-ray diffraction. Crystal data for 1: C22H54As2Ni2P2, Mr = 647.89, monoclinic, I2/a (a nonstandard setting of C2/c, No. 15), a = 16.848 (3) Å, b = 12.069 (1) Å, c = 17.379 (3) Å, β = 114.60 (2)°, U = 3213.2 (5) Å3, Dcalcd = 1.339 g cm–3, Z = 4, λ(Mo Kα) = 0.71069 Å (graphite monochromator), µ(Mo Kα) = 33.24 cm–1, final R = 0.0399 (Rw = 0.0526) from 2245 observed reflections (I > 3σ(I)), 2433 measured. Crystal data for 2: C48H64As2Ni2N4, Mr = 964.34, monoclinic, P21/n (a nonstandard setting of P21/c, No. 14), a = 13.320 (2) Å, b = 12.889 (2) Å, c = 15.042 (3) Å, β = 111.00 (2)°, V = 2410.7 (5) Å3, Dcalcd = 1.328 g cm–3, Z = 2, λ(Mo Kα) = 0.71069 Å (graphite monochromator), μ(Mo Kα) = 21.78 cm–1, final R = 0.0563 (Rw = 0.0657) from 1557 observed reflections (I > 3σ(I)) 1743 measured. 1 contains two 16-electron Ni(I) atoms bridged by two t-Bu2As groups and linked by a single Ni–Ni bond (Ni–Ni = 2.429 (1) Å). A crystallographically imposed twofold axis passes through each As atom, giving a planar symmetrical central Ni2As2 core. Each Ni atom bears a PMe3 group, which is virtually coplanar with the Ni2As2 plane. In 2 the CN-p-tol groups give each Ni atom a pseudotetrahedral geometry. The central Ni2As2 core is again planar by virtue of a crystallographic center of inversion, which lies at the midpoint of the Ni–Ni bond (Ni–Ni = 2.693 (2) Å). Trends in Ni–Ni bond lengths in these and related complexes are correlated with the electron count on the metal centers and the type of bridging atom.

Original languageEnglish
Pages (from-to)852-856
Number of pages5
JournalInorganic Chemistry
Volume25
Issue number6
DOIs
StatePublished - 1986

Fingerprint Dive into the research topics of 'Synthesis and Structures of Dinuclear Nickel(I) Di-tert-butylarsenido Complexes: X-ray Crystal Structures of [Ni(µ-t-Bu<sub>2</sub>As)(PMe<sub>3</sub>)]<sub>2</sub>(Ni–Ni) and [Ni(µ-t-Bu<sub>2</sub>As)(CN-p-tol)<sub>2</sub>]<sub>2</sub> (Ni–Ni) (tol = Tolyl)'. Together they form a unique fingerprint.

Cite this