title: Two Different Pathways in the Reduction of [(S=)PCl(μ-NtBu)]2 with Na.
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)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-NtBu)]2 (2-) , which is observed in the polymeric structures of three-dimensional [{(S-)ClP(μ-NtBu)2 PCl(S)}Na(Na⋅THF2 )]n (3) and two dimensional [{(S-)ClP(μ-NtBu)2 PCl(S)} (Na⋅THF)2 ]n (4).
authors.affiliation: Department of Chemical Sciences, Indian Institute of Science Education and Research Mohali, Knowledge City, Sector 81, SAS Nagar, Mohali, 140306, Punjab, India.
authors.forename: Deependra
authors.identifier: http://orcid.org/0000-0002-5626-2435
authors.initials: D
authors.lastname: Bawari
authors.affiliation: Department of Chemical Sciences, Indian Institute of Science Education and Research Mohali, Knowledge City, Sector 81, SAS Nagar, Mohali, 140306, Punjab, India.
authors.forename: Billa
authors.identifier: http://orcid.org/0000-0001-7185-3068
authors.initials: B
authors.lastname: Prashanth
authors.affiliation: Department of Chemical Sciences, Indian Institute of Science Education and Research Mohali, Knowledge City, Sector 81, SAS Nagar, Mohali, 140306, Punjab, India.
authors.forename: Satyam
authors.identifier: http://orcid.org/0000-0002-7184-1849
authors.initials: S
authors.lastname: Ravi
authors.affiliation: Department of Chemical Sciences, Indian Institute of Science Education and Research Mohali, Knowledge City, Sector 81, SAS Nagar, Mohali, 140306, Punjab, India.
authors.forename: K R
authors.initials: KR
authors.lastname: Shamasundar
authors.affiliation: Department of Chemical Sciences, Indian Institute of Science Education and Research Mohali, Knowledge City, Sector 81, SAS Nagar, Mohali, 140306, Punjab, India. sanjaysingh@iisermohali.ac.in.
authors.forename: Sanjay
authors.identifier: http://orcid.org/0000-0003-0806-3105
authors.initials: S
authors.lastname: Singh
authors.affiliation: Chemistry Department, Cambridge University, Lensfield Road, Cambridge, CB2 1EW, UK. dsw1000@cam.ac.uk.
authors.forename: Dominic S
authors.initials: DS
authors.lastname: Wright
keywords: biradicaloids; cyclization; macrocycles; phosphazanes; reduction