Coordination chemistry of bis(delta-camphorquinone dioximato)nickel(II) and -palladium(II). Reactions and structural studies of some M/sub 3/Ag/sub 3/ cluster complexes of camphorquinone dioxime

Journal Article · Wed Oct 01 00:00:00 EDT 1980 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic50212a059· OSTI ID:6812692

Ma, M S; Angelici, R J; Powell, D; Jacobson, R A

Reactions of AgNO/sub 3/ with Ni(delta-HCQD)/sub 2/ or Pd(delta-HCQD)/sub 2/, where delta-HCQD/sup -/ is delta-camphorquinone dioximato, yielded the hexanuclear metal cluster complexes (Ni(delta-HCQD)/sub 2/Ag)/sub 3/.2.5CHCl/sub 3/, Ni-Ag, and (Pd(delta-HCQD)/sub 2/Ag)/sub 3/.2CHCl/sub 3/, Pd-Ag, respectively. X-ray crystallographic studies performed on both complexes showed them to belong to space group P2/sub 1/2/sub 1/2/sub 1/. The unit cell dimensions of Ni-Ag are a = 15.990 (5) A, B = 38.44 (1) A, c = 13.437 (5) A, V = 8260.97 A/sup 3/, and Z = 4 while those of Pd-Ag are a = 16.110 (6), b = 38.92 (1), c = 13.393 (3) A, V = 8395.55 A/sup 3/, and Z = 4. Block-diagonal least-squares refinement of 3021 observed reflections for Ni-Ag and 6112 for Pd-Ag converged to R/sub F/ = 10.7 and 11.4 (R/sub w/ = 12.7 and 15.0) for the Ni-Ag and Pd-Ag structures, respectively. Their structures indicate that each hexanuclear molecule consists of three individual M(delta-HCQD)/sub 2//sup -/units which act as multidentate ligands coordinating to a linear chain of three silver atoms. The coordination geometry around each M ion in the M(delta-HCQD)/sub 2//sup -/units is square planar, and the delta-HCQD/sup -/ligands are coordinated to M via N and O atoms. The Ag in the center of the molecule is coordinated to six O atoms with average Ag-O distances of 2.49 (3) and 2.45 (2) A for Ni-Ag and Pd-Ag, respectively. The two silver atoms at the ends of the chain are each coordinated to three nitrogen atoms from the M(delta-HCQD)/sub 2//sup -/ units with average Ag-N distances of 2.20 (4) and 2.27 (3) A, respectively. The Ag-Ag distances, 3.059 (5) and 3.052 (5) A in Ni-Ag and 3.173 (3) and 3.179 (3) A in Pd-Ag, are somewhat longer than those (2.89 A) in Ag metal and indicate that there are Ag-Ag interactions along the linear chains.

• Research Organization: Iowa State Univ., Ames
• OSTI ID: 6812692
• Journal Information: Inorg. Chem.; (United States), Vol. 19:10
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
SILVER COMPLEXES
CHEMICAL REACTIONS
STRUCTURAL CHEMICAL ANALYSIS
NICKEL COMPLEXES
PYRIDINES
PALLADIUM COMPLEXES
BOND ANGLE
BOND LENGTHS
LATTICE PARAMETERS
ORGANIC CHLORINE COMPOUNDS
OXIMES
QUINONES
SILVER NITRATES
X-RAY DIFFRACTION
AMINES
AROMATICS
AZINES
COHERENT SCATTERING
COMPLEXES
DIFFRACTION
DIMENSIONS
HETEROCYCLIC COMPOUNDS
HYDROXY COMPOUNDS
LENGTH
NITRATES
NITROGEN COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXYGEN COMPOUNDS
SCATTERING
SILVER COMPOUNDS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)