Two Different Pathways in the Reduction of [(S=)PCl(μ‐N t Bu)] 2 with Na

Reduction of the cyclodiphosphazane [(S=)ClP(μ‐N t Bu)] 2 ( 1 ) with sodium metal in refluxing toluene proceeds via two different pathways. One is a Wurtz‐type pathway involving elimination of NaCl from 1 followed by head‐to‐tail cyclization to give the hexameric macrocycle [(μ‐S)P(μ‐N t Bu) 2 P(=S)] 6 ( 2 ). The other pathway involves reduction of the P=S bonds of 1 to generate colorless singlet biradicaloid dianion trans ‐[S−P(Cl)(μ‐N t Bu)] 2 2− , which is observed in the polymeric structures of three‐dimensional [{(S−)ClP(μ‐N t Bu) 2 PCl(S)}Na(Na ⋅ THF 2 )] n ( 3 ) and two dimensional [{(S−)ClP(μ‐N t Bu) 2 PCl(S)} (Na ⋅ THF) 2 ] n ( 4 ).