TY - JOUR
T1 - Dispersion force stabilized two-coordinate transition metal-amido complexes of the -N(SiMe3)Dipp (Dipp = C6H3-2,6-Pr i2) ligand
T2 - Structural, spectroscopic, magnetic, and computational studies
AU - Lin, Chun Yi
AU - Guo, Jing Dong
AU - Fettinger, James C.
AU - Nagase, Shigeru
AU - Grandjean, Fernande
AU - Long, Gary J.
AU - Chilton, Nicholas F.
AU - Power, Philip P.
PY - 2013/12/2
Y1 - 2013/12/2
N2 - A series of high spin, two-coordinate first row transition metal-amido complexes, M{N(SiMe3)Dipp}2 {M = Fe (1), Co (2), or Ni (3); Dipp = C6H3-2,6-Pri2} and a tetranuclear C-H activated chromium amide, [Cr{N(SiMe2CH 2)Dipp}2Cr]2(THF) (4), were synthesized by reaction of their respective metal dihalides with 2 equiv of the lithium amide salt. They were characterized by X-ray crystallography, electronic and infrared spectroscopy, SQUID magnetic measurements, and computational methods. Contrary to steric considerations, the structures of 1-3 display planar eclipsed M{NSiC(ipso)}2 arrays and short M-N distances. DFT calculations, corrected for dispersion effects, show that dispersion interactions involving C-H-H-C moieties likely stabilize the structures by 21.1-29.4 kcal mol -1, depending on the level of the calculations employed. SQUID measurements confirm high spin electron configurations for all the complexes and substantial orbital contributions for 1 and 2.
AB - A series of high spin, two-coordinate first row transition metal-amido complexes, M{N(SiMe3)Dipp}2 {M = Fe (1), Co (2), or Ni (3); Dipp = C6H3-2,6-Pri2} and a tetranuclear C-H activated chromium amide, [Cr{N(SiMe2CH 2)Dipp}2Cr]2(THF) (4), were synthesized by reaction of their respective metal dihalides with 2 equiv of the lithium amide salt. They were characterized by X-ray crystallography, electronic and infrared spectroscopy, SQUID magnetic measurements, and computational methods. Contrary to steric considerations, the structures of 1-3 display planar eclipsed M{NSiC(ipso)}2 arrays and short M-N distances. DFT calculations, corrected for dispersion effects, show that dispersion interactions involving C-H-H-C moieties likely stabilize the structures by 21.1-29.4 kcal mol -1, depending on the level of the calculations employed. SQUID measurements confirm high spin electron configurations for all the complexes and substantial orbital contributions for 1 and 2.
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U2 - 10.1021/ic402105m
DO - 10.1021/ic402105m
M3 - Article
AN - SCOPUS:84889252682
SN - 0020-1669
VL - 52
SP - 13584
EP - 13593
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 23
ER -