Crystal and molecular structure of pentakis(4-methyl-1-phospha-2,6,7-trioxabicyclo(2. 2. 2)octane)cobalt(I)(acetonitrile)trinitratocobalt(II), Co(P(OCH/sub 2/)/sub 3/CMe)/sub 5/ (Co(NO/sub 3/)/sub 3/NCMe)

Journal Article · Fri Jul 01 04:00:00 EDT 1977 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic50173a001· OSTI ID:7214904

Albright, J O; Clardy, J C; Verkade, J G

Unlike PR/sub 3/ ligands which readily form ONCo(PR/sub 3/)/sub 3/ upon reaction with Co(NO/sub 3/)/sub 2/ in i-PrOH, P(OCH/sub 2/)/sub 3/CMe(L) induces disproportionation of divalent cobalt to form red (CoL/sub 5/)/sub 2/Co(NO/sub 3/)/sub 4/) (1) and purple (CoL/sub 6/)/sub 2/(Co(NO/sub 3/)/sub 4/)/sub 3/ (2). Evidence for the nitrosyl complex ONCo(P(CH/sub 2/O)/sub 3/CMe)/sub 3/ (3) is presented in the case of the caged phosphine ligand, however. Attempted recrystallization of 1 from hot acetonitrile results in the formation of red (CoL/sub 5/)(Co(NO/sub 3/)/sub 3/NCMe) (4) and yellow (CoL/sub 5/)NO/sub 3/. The crystal and molecular structure of the title compound 4 was determined from three-dimensional single-crystal x-ray data. The compound crystallizes in the orthorhombic space group Pbca with a = 22.578 (3), b = 17.224 (5), and c = 25.961 (9) A and eight molecules per unit cell. The structure was solved by conventional heavy-atom techniques and refined on F by least-squares methods to weighted and unweighted R factors of 0.091 and 0.111, respectively, for 3944 independent nonzero reflections. The cation consists of a near-perfect trigonal-bipyramidal array of P atoms around the monovalent cobalt with an average CoP distance of 2.128 (3) A. Distances and angles associated with the ligand are very comparable to those recently reported for P(OCH/sub 2/)/sub 3/CH/sub 2/Br. The anion has a novel heptacoordinate cobalt(II) geometry which incorporates three bidentate nitrates and an acetonitrile molecule. The axial OCoN angle is 178.9/sup 0/ while the OCoO angles in the somewhat distorted equatorial plane range from 57.9 to 93.4/sup 0/. The axial (2.160 A) and equatorial (average 2.165 A) CoO bond distances are nearly equal.

• Research Organization: Ames Lab., IA
• OSTI ID: 7214904
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 16:7; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL REACTIONS
COBALT COMPLEXES
COMPLEXES
CRYSTAL STRUCTURE
LIGANDS
MOLECULAR STRUCTURE
NITRILES
NITRO COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDATION
PHOSPHORUS COMPOUNDS
REDUCTION
TRANSITION ELEMENT COMPLEXES