Dispersion Force Stabilized Two-coordinate Transition Metal-Amido Complexes of the -N(SiMe₃)Dipp (Dipp = C₆H₃-2,6-Pri₂) Ligand: Structural, Spectroscopic, Magnetic, and Computational Studies

Chun-Yi Lin; Jingdong Guo; James C. Fettinger; Shigeru Nagase; Fernande Grandjean; Gary J. Long; Nicholas F. Chilton; Philip P. Power

doi:10.1021/ic402105m

Dispersion Force Stabilized Two-coordinate Transition Metal-Amido Complexes of the -N(SiMe₃)Dipp (Dipp = C₆H₃-2,6-Prⁱ₂) Ligand: Structural, Spectroscopic, Magnetic, and Computational Studies

Chun-Yi Lin
, Jingdong Guo
, James C. Fettinger
, Shigeru Nagase
, Fernande Grandjean
, Gary J. Long
, Nicholas F. Chilton
, Philip P. Power

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

A series of high spin, two-coordinate first row transition metal–amido complexes, M{N(SiMe ₃ )Dipp} ₂ {M = Fe ( 1 ), Co ( 2 ), or Ni ( 3 ); Dipp = C ₆ H ₃ -2,6-Pr ⁱ ₂ } and a tetranuclear C–H activated chromium amide, [Cr{N(SiMe ₂ CH ₂ )Dipp} ₂ Cr] 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 .

Original language	American English
Journal	Inorganic Chemistry
Volume	52
DOIs	https://doi.org/10.1021/ic402105m
State	Published - Dec 1 2013

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Chemistry

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Lin, C.-Y., Guo, J., Fettinger, J. C., Nagase, S., Grandjean, F., Long, G. J., Chilton, N. F., & Power, P. P. (2013). Dispersion Force Stabilized Two-coordinate Transition Metal-Amido Complexes of the -N(SiMe₃)Dipp (Dipp = C₆H₃-2,6-Prⁱ₂) Ligand: Structural, Spectroscopic, Magnetic, and Computational Studies. Inorganic Chemistry, 52. https://doi.org/10.1021/ic402105m

Dispersion Force Stabilized Two-coordinate Transition Metal-Amido Complexes of the -N(SiMe₃)Dipp (Dipp = C₆H₃-2,6-Prⁱ₂) Ligand: Structural, Spectroscopic, Magnetic, and Computational Studies. / Lin, Chun-Yi; Guo, Jingdong; Fettinger, James C. et al.
In: Inorganic Chemistry, Vol. 52, 01.12.2013.

Research output: Contribution to journal › Article › peer-review

@article{5f09227e30bc40119bb3207ac3221803,

title = "Dispersion Force Stabilized Two-coordinate Transition Metal-Amido Complexes of the -N(SiMe₃)Dipp (Dipp = C₆H₃-2,6-Pri₂) Ligand: Structural, Spectroscopic, Magnetic, and Computational Studies",

abstract = " A series of high spin, two-coordinate first row transition metal–amido complexes, M\{N(SiMe 3 )Dipp\} 2 \{M = Fe ( 1 ), Co ( 2 ), or Ni ( 3 ); Dipp = C 6 H 3 -2,6-Pr i 2 \} and a tetranuclear C–H activated chromium amide, [Cr\{N(SiMe 2 CH 2 )Dipp\} 2 Cr] 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 .",

author = "Chun-Yi Lin and Jingdong Guo and Fettinger, \{James C.\} and Shigeru Nagase and Fernande Grandjean and Long, \{Gary J.\} and Chilton, \{Nicholas F.\} and Power, \{Philip P.\}",

year = "2013",

month = dec,

day = "1",

doi = "10.1021/ic402105m",

language = "American English",

volume = "52",

journal = "Inorganic Chemistry",

}

TY - JOUR

T1 - Dispersion Force Stabilized Two-coordinate Transition Metal-Amido Complexes of the -N(SiMe₃)Dipp (Dipp = C₆H₃-2,6-Pri₂) Ligand: Structural, Spectroscopic, Magnetic, and Computational Studies

AU - Lin, Chun-Yi

AU - Guo, Jingdong

AU - Fettinger, James C.

AU - Nagase, Shigeru

AU - Grandjean, Fernande

AU - Long, Gary J.

AU - Chilton, Nicholas F.

AU - Power, Philip P.

PY - 2013/12/1

Y1 - 2013/12/1

N2 - A series of high spin, two-coordinate first row transition metal–amido complexes, M{N(SiMe 3 )Dipp} 2 {M = Fe ( 1 ), Co ( 2 ), or Ni ( 3 ); Dipp = C 6 H 3 -2,6-Pr i 2 } and a tetranuclear C–H activated chromium amide, [Cr{N(SiMe 2 CH 2 )Dipp} 2 Cr] 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(SiMe 3 )Dipp} 2 {M = Fe ( 1 ), Co ( 2 ), or Ni ( 3 ); Dipp = C 6 H 3 -2,6-Pr i 2 } and a tetranuclear C–H activated chromium amide, [Cr{N(SiMe 2 CH 2 )Dipp} 2 Cr] 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 .

UR - https://scholarsmine.mst.edu/chem_facwork/2064

UR - https://doi.org/10.1021/ic402105m

U2 - 10.1021/ic402105m

DO - 10.1021/ic402105m

M3 - Article

VL - 52

JO - Inorganic Chemistry

JF - Inorganic Chemistry

ER -

Dispersion Force Stabilized Two-coordinate Transition Metal-Amido Complexes of the -N(SiMe₃)Dipp (Dipp = C₆H₃-2,6-Prⁱ₂) Ligand: Structural, Spectroscopic, Magnetic, and Computational Studies

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