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Ambient‐Temperature Synthesis of 2‐Phosphathioethynolate, PCS – , and the Ligand Properties of ECX – (E = N, P; X = O, S)
Author(s) -
Jupp Andrew R.,
Geeson Michael B.,
McGrady John E.,
Goicoechea Jose M.
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201501075
Subject(s) - chemistry , cyanate , thiocyanate , ligand (biochemistry) , ion , coordination sphere , nitrogen , crystallography , tungsten , coordination complex , sulfur , inorganic chemistry , medicinal chemistry , stereochemistry , metal , crystal structure , polymer chemistry , organic chemistry , biochemistry , receptor
A synthesis of the 2‐phosphathioethynolate anion, PCS – , under ambient conditions is reported. The coordination chemistry of PCO – , PCS – and their nitrogen‐containing congeners is also explored. Photolysis of a solution of W(CO) 6 in the presence of PCO – [or a simple ligand displacement reaction using W(CO) 5 (MeCN)] affords [W(CO) 5 (PCO)] – ( 1 ). The cyanate and thiocyanate analogues, [W(CO) 5 (NCO)] – ( 2 ) and [W(CO) 5 (NCS)] – ( 3 ), are also synthesised using a similar methodology, allowing for an in‐depth study of the bonding properties of this family of related ligands. Our studies reveal that, in the coordination sphere of tungsten(0), the PCO – anion preferentially binds through the phosphorus atom in a strongly bent fashion, while NCO – and NCS – coordinate linearly through the nitrogen atom. Reactions between PCS – and W(CO) 5 (MeCN) similarly afford [W(CO) 5 (PCS)] – ; however, due to the ambidentate nature of the anion, a mixture of both the phosphorus‐ and sulfur‐bonded complexes ( 4a and 4b , respectively) is obtained. It was possible to establish that, as with PCO – , the PCS – ion also coordinates to the metal centre in a bent fashion.