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. 2023 May 11;3(4):217-222.
doi: 10.1021/acsorginorgau.3c00010. eCollection 2023 Aug 2.

Nickel Complexes of Allyl and Vinyldiphenylphosphine

Marissa L Clapson  1 , David J Nelson  2 , Marcus W Drover  1
Affiliations

Nickel Complexes of Allyl and Vinyldiphenylphosphine

Marissa L Clapson et al. ACS Org Inorg Au. .

Abstract

Monodentate phosphine-ligated nickel compounds, e.g., [Ni(PPh3)4] are relevant as active catalysts across a broad range of reactions. This report expands upon the coordination chemistry of this family, offering the reactivity of allyl- and vinyl-substituted diphenylphosphine (PPh2R) with [Ni(COD)2] (COD = 1,5-cyclooctadiene). These reactions provide three-coordinate dinickelacycles that are intermolecularly tethered through adjacent {Ni}-olefin interactions. The ring conformation of such cycles has been studied in the solid-state and using theoretical calculations. Here, a difference in reaction outcome is linked to the presence of an allyl vs vinyl group, where the former is observed to undergo rearrangement, bringing about challenges in clean product isolation.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Chart 1
Chart 1. Nickel Olefin Compounds and Six-Membered Ring Conformations Described Herein
Figure 1
Figure 1
Synthesis of [NiIIBr2(PR3)2] complexes. Inset shows X-ray molecular structure of 2. Thermal ellipsoids are shown at the 50% probability level. Hydrogen atoms have been omitted for clarity. Selected bond distances (Å) and angles (deg): Ni1–Br1, 2.308(2); Ni1–P1, 2.2342(7); Br1–Ni1–Br2, 180.0; P1–Ni1–P2, 180.0.
Figure 2
Figure 2
Synthesis of a six-membered nickelacycle Ni η2-vinyl dimer 3 featuring a boat conformation. Inset shows the X-ray molecular structure depiction of 3 including the core ring structure. Selected bond distances (Å) and angles (deg): Ni1–P1, 2.192(2); Ni1–P2, 2.145(2); Ni2–P3, 2.192(2); Ni2–P4, 2.148(2); Ni1–C1, 1.983(8); Ni1–C2, 1.964(8); Ni2–C3, 1.953(8), Ni2–C4, 1.973(8); P1–Ni1–P2, 115.7(11); C1–Ni1–C2, 42.4(3); P3–Ni2–P4, 116.1(1); C3–Ni2–C4, 42.8(3).
Figure 3
Figure 3
Structure of [Pd(PPh2CHCH2)(PPh2-η2-CHCH2)]22+ (CCDC Accession code: JEPPOJ). Adapted from ref (18). Copyright 1990 American Chemical Society.
Figure 4
Figure 4
Synthesis of a six-membered Ni η2-allyl dimer 5. Inset shows the X-ray molecular structure of 5. Selected bond distances (Å) and angles (deg): Ni1–P1, 2.1891(9); Ni1–P2, 2.1450(8); Ni2–P3, 2.1450(8); Ni2–P4, 2.1891(9); Ni1–C1, 1.972(3); Ni1–C2, 1.964(3); Ni2–C3, 1.964(3), Ni2–C4, 1.972(3); P1–Ni1–P2, 108.80(4); C1–Ni1–C2, 42.2(1); P3–Ni2–P4, 108.80(4); C3–Ni2–C4, 42.2(1).
Figure 5
Figure 5
Boat and chair ring conformations for {Ni}2 compounds. Energies calculated using DLPNO-CCSD(T)/cc-pVTZ/SMD(benzene) (see the SI for computational details).
Figure 6
Figure 6
Reaction of 3 with HBCy2. Inset shows the 31P{1H} NMR spectrum (203 MHz, C6D6, 298 K).
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