POLYTERTIARY PHOSPHINES AND ARSINES II: Systematics of Polytertiary Phosphines and their Metal Complexes

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Abstract
The geometries of possible polytertiary phosphine networks containing trivalent phosphorus atoms and bridging groups are shown to be completely analogous to the geometries of acyclic planar networks of linked sp 2 carbon atoms.2 The bridging groups between pairs of phosphorus atoms in such polytertiary phosphines may be classified into the following three types on the basis of coordination properties: (1) Bridges which allow the two bridged phosphorus atoms to bond both to a single metal atom but not to different metal atoms (type 1); (2) Bridges which allow the two bridged phosphorus atoms to bond to two different metal atoms but not both to a single metal atom (type 2); and (3) Bridges which allow the two bridged phosphorus atoms to bond either to two different metal atoms or both to a single metal atom (type 3). The numbers of possible polytertiary phosphines with up to six phosphorus atoms and various combinations of these three types of bridges are determined. The modes of coordination of the possible tritertiary phosphines and the possible tripod and linear tetratertiary phosphines to one or more metal atoms are given.