Synthesis, crystal, and molecular structure of paramagnetic tri-t-butylphosphonium tribromo(tri-t-butylphosphine)nickelate(II)
- 1 January 1975
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 13,p. 1294-1298
- https://doi.org/10.1039/dt9750001294
Abstract
Reaction of tri-t-butylphosphine with nickel(II) bromide in alcoholic solution yielcs green [But 3PH][(But 3P)NiBr3]. Conductivity, magnetic-susceptibility, and electronic spectral measurements, and X-ray single-crystal analysis indicated the structure to be the same in solution as in the solid state. Crystals are monoclinic, space group Cc. with cell dimensions a= 24·069(3), b= 13·896(4), c= 18·739(2)Å, β= 14891(1)°, Z= 4. The structure was solved by conventional heavy-atom methods and refined to R 0·088 for 1 839 observed reflexions. Structural data for the paramagnetic anion, which has nearly C3v symmetry (excluding the butyl groups), particularly reflect the bulkiness of the But 3P ligand; mean dimensions: Br–Ni–Br 108·7°, P–C 2·02(10) and Ni–Br 2·38(2)Å, and a Ni–P bond length of 2·48(1)Å. The calculated Ni–PBut 3 cone angle is 180 ± 2°. The P(2)–H bond of the cation lies near the pseudo C3 axis of the anion so that Ni⋯P(2) is 4·48 Å, with P(2)⋯Br 4·27–4-31 Å. These interion contacts indicate strong ion-pairing interaction in the solid-state structure.Keywords
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