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Metal‐Mediated Conversion of Methylcycloarsoxane (CH 3 AsO) n to Macrocyclic Octa‐ and Decanuclear Ligands –Trigonal Bipyramidal Coordination of Trivalent Arsenic
Author(s) -
Müller Iris M.,
Sheldrick William S.
Publication year - 1998
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/(sici)1099-0682(199812)1998:12<1999::aid-ejic1999>3.0.co;2-t
Subject(s) - chemistry , trigonal bipyramidal molecular geometry , acetonitrile , coordination sphere , metal , arsenic , crystallography , coordination complex , bipyramid , trigonal prismatic molecular geometry , trigonal crystal system , stereochemistry , inorganic chemistry , medicinal chemistry , crystal structure , organic chemistry , octahedron
Reaction of cyclo‐ (CH 3 AsO) n with MCl 3 · x H 2 O in acetonitrile at 100 °C affords [MCl 2 { cyclo‐ (CH 3 AsO) 8 }] [M = Ru ( 1 ), M = Os ( 2 )] in which cyclooctamers (CH 3 AsO) 8 are stabilised in a ĸ 4 As 1,3,5,7 binding mode in the equatorial coordination sphere of the Group 8 metals. In contrast treatment of K 2 PtCl 4 with alternatively AgNO 3 or Ag 2 CO 3 and cyclo‐ (CH 3 AsO) n at 100 °C in the same solvent leads to the formation of respectively octa‐ or decanuclear cagelike ligands in [Pt 2 {[ cyclo‐ (As[CH 3 ]OAs[NC(O)CH 3 ]O) 2 ] 2 }] ( 3 ) and [Pt 2 {[{CH 3 C(O)N} 2 As 5 (CH 3 ) 5 O 4 ] 2 }] ( 4 ) by metal‐assisted reactions between cyclo‐ (CH 3 AsO) n and acetonitrile. λ 5 ‐As III atoms in these complexes participate in square‐planar Pt II coordination and themselves exhibit distorted trigonal bipyramidal coordination geometries.