Two Different Pathways in the Reduction of [(S=)PCl(μ‐NtBu)]2 with Na |
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| Authors: | Deependra Bawari Dr Billa Prashanth Satyam Ravi Dr K R Shamasundar Dr Sanjay Singh Prof Dominic S Wright |
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| Institution: | 1. Department of Chemical Sciences, Indian Institute of Science Education and Research Mohali, Punjab, India;2. Chemistry Department, Cambridge University, Cambridge, UK |
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| Abstract: | Reduction of the cyclodiphosphazane (S=)ClP(μ‐NtBu)]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‐NtBu)2P(=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‐NtBu)]22?, which is observed in the polymeric structures of three‐dimensional {(S?)ClP(μ‐NtBu)2PCl(S)}Na(Na ? THF2)]n ( 3 ) and two dimensional {(S?)ClP(μ‐NtBu)2PCl(S)} (Na ? THF)2]n ( 4 ). |
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| Keywords: | biradicaloids cyclization macrocycles phosphazanes reduction |
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