Steric titration of arylthiolate coordination modes at pseudotetrahedral nickel(II) centers.
Several derivatives of the pseudotetrahedral phenylthiolate complex Tp(Me,Me)Ni-SPh (1), Tp(Me,Me-) = hydrotris(3,5-dimethyl-1-pyrazolyl)borate, were prepared incorporating substituted arylthiolates, including a series of ortho-substituted ligands Tp(Me,Me)Ni-SR (R = 2,6-Me(2)C(6)H(3), 2; 2,4,6-Me(3)C(6)H(2), 3; 2,4,6- (i)Pr(3)C(6)H(2), 4; and 2,6-Ph(2)C(6)H(3), 5) and a series of para-substituted complexes (R = C(6)H(4)-4-OMe, 6; C(6)H(4)-4-Me, 7; and C(6)H(4)-4-Cl, 8). The products were characterized by (1)H NMR and UV-vis spectroscopy. Spectra of 6-8 were consistent with retention of a common structure across the para-substituted series with modest perturbation of the spectral features of 1 assisting their assignment. In contrast, spectra of 2-5 were indicative of a significant change in configuration across the ortho-disubstituted series. The structure of complex 5 was determined by X-ray crystallography and a distinctive arylthiolate ligation mode was found, in which the N(3)S ligand field was significantly distorted toward a sawhorse, compared to a more common trigonal pyramidal shape (e.g., 1). Moreover, the arylthiolate substituent rotated from a vertical orientation co-directional with the pyrazole rings and disposed between two of them in 1, to a horizontal orientation perpendicular to and over a single pyrazole ring in 5. This reorientation is necessary to accommodate the large ortho substituents of the latter complex. The divergent Ni-S coordination modes result in distinct (1)H NMR and electronic spectra that were rationalized by density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. These results demonstrate rich coordination chemistry for arylthiolates that can be elicited by steric manipulation at the periphery of pseudotetrahedral ligand fields.
Chattopadhyay
Swarup
S
Department of Chemistry and Biochemistry, Ohio University, Athens, Ohio 45701, USA.
Deb
Tapash
T
Petersen
Jeffrey L
JL
Young
Victor G
VG
Jensen
Michael P
MP
D018360:Crystallography, X-Ray; D006841:Hydrocarbons, Aromatic / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D009532:Nickel / Q000737:chemistry*; D011789:Quantum Theory; D013053:Spectrophotometry; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000737:chemistry*
D006841:Hydrocarbons, Aromatic; D013438:Sulfhydryl Compounds; D009532:Nickel