Organometallic trinuclear niobium cluster complex in aqueous solution: synthesis and characterization of niobium complexes containing Nb(3)(mu-eta(2):eta(2)( perpendicular)-NCCH(3))(mu(2)-O)(3)(6+) cluster core.
The synthesis and characterization of an organometallic trinuclear oxo-bridged niobium cluster complex with perpendicularly coordinated mu(3)-eta(2):eta(2)( perpendicular)-acetonitrile ligand in aqueous solution is reported. Reaction of NbCl(5) in acetonitrile with aluminum under argon followed by reaction with aqueous hydrochloric acid affords, after suitable workup, the isolation of the organometallic [Nb(3)(mu-eta(2):eta(2)-NCCH(3))O(3)(H(2)O)(9)](6+) aqua ion by cation-exchange chromatography. The purple niobium aqua ion in 2 M HCl shows a small peak at 365 nm (epsilon approximately 511 M(-1) cm(-1) per Nb) and a broad peak at 565 nm (epsilon approximately 335 M(-1) cm(-1)) in the UV-visible region. It is electron paramagnetic resonance (EPR)-active (g = 1.98), but no hyperfine interaction with the (93)Nb nuclear spin (I = 9/2) was observed. The cyclic voltammogram of [Nb(3)(mu-eta(2):eta(2)-NCCH(3))O(3)(H(2)O)(9)](6+) in 4 M HCl on edge-plane pyrolytic graphite electrode at 50 mV s(-1) in the potential range -1.2 V to +1.1 V (vs SCE) exhibits three anodic peaks at -0.12, +0.53, and +0.85 V and a large cathodic peak at -0.91 V with a slight shoulder at about -0.8 V. The purple aqua ion reacted with potassium thiocyanate to give the green thiocyanate derivative, which was crystallized as ((CH(3))(3)NH)(3)[Nb(3)(mu-eta(2):eta(2)-NCCH(3))O(3)(NCS)(9)].2.5H(2)O (1) and subjected to X-ray structure analysis. Density-functional theory (DFT) calculations fully supported the structure of the cluster.
Department of Chemistry, Technical University of Denmark, Building 207, Kemitorvet, 2800 Lyngby, Denmark.
Hans Arni Nybo
HA
Joensen
Gro Kallehave
GK
Hansson
Svetlana G
SG
Kozlova
Artem L
AL
Gushchin
Inger
I
Søtofte
Bee-Lean
BL
Ooi