Synthesis, Properties, and Solid-State Structures of Bis(alkyne)metal(0) Complexes (Metal = Ni, Pt) with Substituted Alkynediols and Alkynols

Abstract

A variety of tetrasubstituted alkynediols react with (cdt)Ni (cdt = 1.5.9-cyclododecatriene) to give the homoleptic (alkyne)nickel complexes (HOR1R2CC⋮CCR1R2OH)2Ni as yellow crystals that are stable in the solid state at room temperature (R1 = R2 = Et, 1; R1 = Me, R2 = Et, 2; R1 = Me, R2 = Pr, 3; R1 = R2 = −(CH2)5−, 4; R1 = Me, R2 = i-Bu, 5). The 13C-NMR spectra show resonances for the coordinated alkyne carbon nuclei in the 133.5−135.2 ppm region. Only one resonance was found for 1−4 indicating a symmetrical structure. More than one resonance was found for 5 as well as for its platinum analog, compound 8, indicating the presence of different isomeric bis(alkyne)metal complexes. The structure of 1 has been established by single-crystal X-ray diffraction. The central atom is tetrahedrally coordinated to the four carbon atoms of two terminal alkynes. The network of hydrogen bonding between the four OH groups of neighboring molecules, which consists exclusively of intermolecular hydrogen bonds, stabilizes the crystal structure yielding a polymer-like chain. The platinum complex 9 (R1 = R2 = Me) shows similar structural properties. The reaction of (cdt)Ni or (cod)2Pt (cod = 1.5-cyclooctadiene) with the substituted alkynols R3CC⋮CCR1 2OH yields the new bis(alkyne)metal(0) compounds 10 (M = Ni, R = Me, R1 = Me), 11 (M = Pt, R = Me, R1 = Me), and 12 (M = Ni, R = Me, R1 = Et). Single-crystal X-ray structure determinations of 10−12 reveal that the central metal atoms are tetrahedrally coordinated by the four carbon atoms of the alkyne ligands. Two (alkyne)2M units are connected via hydrogen bonds between the four OH groups to form a dimer in the solid state. Complex 10 reacts in solution below −15 °C to yield the trimeric complex (alkyne)4Ni3.

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“…Of particular interest are oligomeric, cluster, alkyne–platinum(0) complexes. Whereas some homoleptic Pt 0 complexes of the [Pt(alkyne) 2 ]4–9 and [Pt 2 (alkyne) 3 ] types10 are known, their respective homoleptic complexes that involve dichelating dialkynes have not hitherto been synthesized but are attractive neutral platinum clusters for application in catalysis.…”

Platinum organometallic compounds: classification and analysis of crystallographic and structural data. Part I. Monomeric Pt(0) and partly of Pt(II) with PtC4, PtA3B and PtC2A2 chromophores

“…In another six species (Dubey 1975, Green et al 1976, Walther et al 1996, Braga et al 1997, there are two bidentate alkyne ligands R 1 C ≡ CR 2 where R 1 R 2 Ph (Green et al 1976 ), Et 2 C(OH) (Dubey 1975 ), Me 2 C(OH) (Walther et al 1996 ); R 1 Ph and R 2 Me 2 C(OH) (Braga et al 1997 ), C 5 H 4 (OH) and Me 3 C (Braga et al 1997 ); and Me 3 C and Me 2 C(OH) (Walther et al 1996 ). These ligands form an essentially tetrahedral environment about each Pt(0) atom.…”

Unique Metal‐Diyne, ‐Enyne, and ‐Enediyne Complexes: Part of the Remarkably Diverse World of Metal‐Alkyne Chemistry

“…However, cyclotriyne ligands have been shown to react (cod) 2 Ni, where cod¼1,5-cyclooctadiene, to give Ni(0)-tris(alkyne) macrocyclic p complexes (344). In 1996, Walther et al (345,346) …”