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Synthetic and structural Studies on Organomolybdenum‐Bismuth Halide Complexes
Author(s) -
Errington R. John,
Fisher George A.,
Norman Nicholas C.,
Guy Orpen A.,
Stratford Susan E.
Publication year - 1994
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.19946200309
Subject(s) - bromine , chemistry , bismuth , halogen , bromide , trigonal bipyramidal molecular geometry , crystallography , molecule , halide , crystal structure , stereochemistry , medicinal chemistry , inorganic chemistry , organic chemistry , alkyl
The reactions between either BiBr 2 Ph and Na/K[Mo(CO) 3 (ηC 5 H 5 )], [BiPh{Mo(CO) 3 (ηC 5 H 5 )} 2 ] and BiBr 2 Ph, or BiBr 3 and BiPh 3 and [Bi{Mo(CO) 3 (ηC 5 H 5 )} 3 ] afford the complex [BiBrPh{Mo(CO) 3 (ηC 5 H 5 )}] 1 which has been characterised by X‐ray crystallography. Complex 1 comprises a bismuth centre bonded to a bromine atom, a phenyl group and a Mo(CO) 3 (ηC 5 H 5 ) fragment together with a longer secondary intermolecular interaction between a bromine from an adjacent molecule which results in a one‐dimensional polymeric structure. Addition of a source of bromide anion to 1 affords the anionic complex [BiBr 2 Ph{Mo(CO) 3 (ηC 5 H 5 )}] − 3 − although prolonged reaction results in the complex [BiBr 2 {Mo(CO) 3 (ηC 5 H 5 )} 2 ] − 5 − which was characterised by X‐ray crystallography as its [Ph 4 P] + salt. Complex 5 − comprises a mononuclear bismuth centre bonded to two bromine atoms and two Mo(CO) 3 (ηC 5 H 5 ) fragments in a geometry which lies between equatorially vacant trigonal bipyramidal and tetrahedral. The complex [PPN] 2 [Bi 2 Cl 6 {Mo(CO) 3 (ηC 5 H 5 )} 2 ] 8 has also been synthesised and characterised by X‐ray crystallography. A dimeric dianion is observed which can be viewed as two edge‐shared square‐based pyramids with chlorine atoms in the basal planes and Mo(CO) 3 (ηC 5 H 5 ) fragments in the apical positions on opposite sides of the Bi 2 Cl 6 plane.