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Synthesis and X‐Ray Analysis of a Nickel Triphenyl‐Cyclopropenyl Complex. A mo‐interpretation of the geometry and bonding in the (C 3 H 3 )ML 3 ‐type of complexes
Author(s) -
Mealli Carlo,
Midollini Stefano,
Moneti Simonetta,
Albright Thomas A.
Publication year - 1983
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19830660216
Subject(s) - chemistry , monoclinic crystal system , ligand (biochemistry) , nickel , crystallography , molecule , metal , crystal structure , derivative (finance) , stereochemistry , receptor , organic chemistry , financial economics , economics , biochemistry
The reaction of [(C 3 Ph 3 )Ni(PPh 3 ) 2 ]ClO 4 with P(CH 2 CH 2 PPh 2 ) 3 (pp 3 ) and NaBPh 4 yields the [(C 3 Ph 3 )Ni(pp 3 )]BPh 4 ‐complex. After long exposure of the solution of this compound in acetone/butanol to the air a new derivative [(C 3 Ph 3 )‐Ni(pp 2 po)]BPh 4 · 0.5 C 4 H 9 OH, where pp 2 po is (Ph 2 PCH 2 CH 2 ) 2 P(CH 2 CH 2 POPh 2 ), is obtained. Complete X‐ray analysis has been carried out for the latter complex: a =18.303 (5); b =29.445 (6), c =13.305 (5) Å, β=112.70 (9)°; space group monoclinic, P 2 1 / a, Z =4. Disorder problems were encountered in the refinement of the structure. The best R is 0.093. One of the arms of the parent pp 3 ‐molecule, not coordinated to the metal, undergoes oxidation. The Ni‐atom, coordinated by the three remaining P‐atoms of the ligand, is also linked in a roughly η 3 ‐mode to the cyclopropenium ligand. The geometry of the molecule is examined in detail. Extended HMO‐calculations were performed to interpret how the variation of PNiP angles affects the bonding between the NiP 3 ‐ and C 3 H 3 ‐fragments. The conclusion is that the overall energy of the complex may be lowered in spite of a weakening of the Ni‐cyclopropenium linkage. Extensions are made to other systems containing a linkage between a metal and a X 3 ‐ring (X=P,As).