Lanthanide tetramethoxyborate complexes isolated from reductive amination of 2,6-diformyl-p-cresol

Journal Article · Wed Apr 14 00:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00060a020· OSTI ID:6465983

Matthews, K D; Kahwa, I A ^[1]; Johnson, M P; Mague, J T; McPherson, G L ^[2]

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1. Univ. of the West Indies, Kingston (Jamaica)
2. Tulane Univ., New Orleans, LA (United States)

Treatment of a hot methanolic solution of 2,6-diformyl-p-cresol (1 mmol), 3,6-dioxa-1,8-octanediamine (2 mmol), and a lanthanide(III) nitrate (1 mmol) with sodium cyanotrihydroborate (1.5 mmol) unexpectedly yields a mixture of isostructural but totally different compounds, [Ln(B(OCH[sub 3])[sub 4])(NO[sub 3])[sub 2](CH[sub 3]OH)[sub 2]], and an asymmetric Schiff base complex, Ln[sub 2]5(NO[sub 3])[sub 4][center dot]1.2CH[sub 3]OH. The lanthanum complex of the B(OCH[sub 3])[sub 4][sup [minus]] anion crystallizes in the monoclinic system. With 1566 unique and 1374 observed (I > 3[sigma](I)) data and 101 variables, R = 0.017 and R[sub w] = 0.025. The structure features an assembly of [La(B(OCH[sub 3])[sub 4])(NO[sub 3])[sub 2](CH[sub 3]OH)[sub 2]][sub n] chains in which La[sup 3+] ions are bridged by bidentate B(OCH[sub 3])[sub 4][sup [minus]] anions which are distorted noticeably from T[sub d] symmetry. The shortest La-O distances in the C[sub 2v] 10-fold 4A,6B-extended dodecahedral coordination polyhedron (two bidentate NO[sub 3][sup [minus]], two methanol molecules, and two bidentate B(OCH[sub 3])[sub 4][sup [minus]]) involve the two B(OCH[sub 3])[sub 4][sup [minus]] anions. The B(OCH[sub 3])[sub 4][sup [minus]] anions form strong bonds with Ln[sup 3+] cations and can achieve the geometrical distortions required for constituting the irregular Ln[sup 3+] coordination polyhedra. As good competitors for Ln[sup 3+] cations, B(OCH[sub 3])[sub 4][sup [minus]] anions can be expected to have destabilizing effects on Schiff base chelates which depend on coordination to Ln[sup 3+] cations to achieve stability. The structure of the Pr[sub 2]5(NO[sub 3])[sub 4][center dot]1.2CH[sub 3]OH complex is reported elsewhere. 29 refs., 3 figs., 3 tabs.

• OSTI ID: 6465983
• Journal Information: Inorganic Chemistry; (United States), Vol. 32:8; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BORON COMPOUNDS
CHEMICAL PREPARATION
LANTHANUM COMPLEXES
AMINATION
CHELATES
CRESOLS
IONS
LATTICE PARAMETERS
METHANOL
MONOCLINIC LATTICES
PRASEODYMIUM COMPLEXES
X-RAY DIFFRACTION
ALCOHOLS
AROMATICS
CHARGED PARTICLES
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DIFFRACTION
HYDROXY COMPOUNDS
ORGANIC COMPOUNDS
PHENOLS
RARE EARTH COMPLEXES
SCATTERING
SYNTHESIS
400201* - Chemical & Physicochemical Properties