A Dinuclear Nickel(II) Complex with Readily Accessible Coordination Sites and Additional N-Functional Groups in Proximity to the Bimetallic Core.
A series of pyrazolate-based dinuclear Ni(II) complexes relevant to the active site of urease are reported. Deprotonation of HL(1) [HL(1) = 3,5-bis(R(2)NCH(2))-pyzH; R(2)N = Me(2)N(CH(2))(3)NMe] by means of 1 equiv of BuLi and subsequent reaction with 2 equiv of [Ni(H(2)O)(6)](ClO(4))(2) in the presence of NEt(i)Pr(2) affords the dinuclear complex [L(1)Ni(2)(OH)(MeCN)(2)](ClO(4))(2) (1). This is shown crystallographically to contain two five-coordinate nickel ions bridged by both the pyrazolate and a hydroxide, with an acetonitrile solvent molecule bound to each metal center. When HL(2) is employed {HL(2) = 3,5-bis(R(2)NCH(2))-pyzH; R(2)N = [Me(2)N(CH(2))(3)](2)N}, the additional ligand side arms act as proton acceptors forming an intramolecular N.H.N bridge to yield the complex [HL(2)Ni(2)(OH)(MeCN)(2)](ClO(4))(3) (2), whose basic bimetallic framework is essentially identical to 1. The two Ni(II) centers in 2 exhibit strong antiferromagnetic coupling (J = -46.7 cm(-)(1)). The labile acetonitrile donors in 2 are easily replaced by either neutral ligands such as dmf or anions such as thiocyanate, giving rise to the formation of complexes [HL(2)Ni(2)(OH)(dmf)(2)](ClO(4))(3) (3) and [HL(2)Ni(2)(OH)(NCS)(2)](ClO(4)) (4), respectively, where the overall dinuclear framework of 2 remains unchanged upon the substitution reaction.
Meyer
Franc
F
Anorganisch-Chemisches Institut der Universität Heidelberg, Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany.
Jacobi
Albrecht
A
Nuber
Bernhard
B
Rutsch
Peter
P
Zsolnai
Laszlo
L