Crystal structures of two unusual, high oxidation state, 16-electron irida­benzenes

Acta Crystallographica Section E: Crystallographic Communications

Zakharov, L.N.¹  Haley, M.M.²  Chase, D.T.³ 

[1] Biochemistry and Materials Science Institute, University of Oregon, Eugene, Oregon 97403-1253, USA;CAMCOR, University of Oregon, 1443 East 13th Avenue, Eugene, Oregon 97403, USA;Department of Chemistry &

关键词: IRIDABENZENE;    METALLABENZENE;    AROMATICITY;    OXIDATION STATE;    COORDINATIVELY UNSATURATED;    CRYSTAL STRUCTURE;   

DOI  :  10.1107/S2056989015018952

学科分类：数学（综合）

来源: International Union of Crystallography

【 摘 要 】

Treatment of carbon­yl(1,2-diphenylpenta-1,3-dien-1-yl-5-yl­idene)bis­(tri­phenyl­phosphane)iridium, [IrCO(—C(Ph)=C(Ph)—CH=CH—CH=)(PPh3)2], with either bromine or iodine produced di­bromido­(1,2-diphenylpenta-1,3-dien-1-yl-5-yl­idene)(tri­phenyl­phosphine)iridium(III), [IrBr2{—C(Ph)=C(Ph)—CH=CH—CH=}(PPh3)], (I), and (1,2-diphenylpenta-1,3-dien-1-yl-5-yl­idene)di­iodido­(tri­phenyl­phosphane)iridium(III), [IrI2{—C(Ph)=C(Ph)—CH=CH—CH=}(PPh3)], (II), respectively, which are two rare examples of 16-electron metalla­benzenes. Structural elucidation of (I) and (II) reveals that these isotypic irida­benzenes are unusual, not only in their electron count, but also in their coordination sphere of the IrIII atom where they contain an apparent open coordination site. The crystal structures of (I) and (II) confirm that the mol­ecules are complexes containing five-coordinated IrIII with only one tri­phenyl­phosphine group bound to the iridium atom, unambiguously proving that the mol­ecules are indeed 16-electron, high-oxidation-state irida­benzenes. The coordination geometry of the IrIII atom in both structures can be best described as a distorted square pyramid with the P, two Br (or I) and one C atom in the basal plane and another C atom in the apical position.

【 授权许可】

CC BY