Abstract
Mononuclear, distorted trigonal bipyramidal [PPN][NiIII(R)- (P(C6H3-3-SiMe3-2-S)3)] (R) Me (1); R) =Et (2)) were prepared by reaction of [PPN][NiIIICl(P(C 6H3-3-SiMe3-2-S)3)] and CH 3MgCl/C2H5MgCl, individually. EPR, SQUID studies as well as DFT computations Reveal that the NiIII in 1 has a low-spin d7 electronic configuration in a distorted trigonal bipyramidal ligand field. The Ni-C bond lengths of 1.994(3) å in 1 and 2.015(3) å in 2 are comparable to that in the NiIII-methyl state of MCR (̃2.04 å) (Sarangi, R.; Dey, M.; Ragsdale, S. W. Biochemistry 2009, 48, 3146). Under a CO atmosphere, CO triggers homolytic cleavage of the NiIII-CH3 bond in 1 to produce Ni II-thiolate carbonyl [PPN][NiII(CO)(P(C6H 3-3-SiMe3-2-S)3)] (3). Additionally, protonation of 1 with phenylthiol generates NiIII-thiolate [PPN][NiIII(SPh)-(P(C6H3-3-SiMe 3-2-S)3)] (4).
| Original language | English |
|---|---|
| Pages (from-to) | 9256-9258 |
| Number of pages | 3 |
| Journal | Journal of the American Chemical Society |
| Volume | 132 |
| Issue number | 27 |
| DOIs | |
| Publication status | Published - 2010 Jul 14 |
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All Science Journal Classification (ASJC) codes
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry
Cite this
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Mononuclear NiIII alkyl complexes (Alkyl = Me and Et) : Relevance to the acetyl-CoA synthase and methyl-CoM reductase. / Lee, Chien Ming; Chen, Chien Hong; Liao, Fu Xing; Hu, Ching Han; Lee, Gene Hsiang.
In: Journal of the American Chemical Society, Vol. 132, No. 27, 14.07.2010, p. 9256-9258.Research output: Contribution to journal › Article
TY - JOUR
T1 - Mononuclear NiIII alkyl complexes (Alkyl = Me and Et)
T2 - Relevance to the acetyl-CoA synthase and methyl-CoM reductase
AU - Lee, Chien Ming
AU - Chen, Chien Hong
AU - Liao, Fu Xing
AU - Hu, Ching Han
AU - Lee, Gene Hsiang
PY - 2010/7/14
Y1 - 2010/7/14
N2 - Mononuclear, distorted trigonal bipyramidal [PPN][NiIII(R)- (P(C6H3-3-SiMe3-2-S)3)] (R) Me (1); R) =Et (2)) were prepared by reaction of [PPN][NiIIICl(P(C 6H3-3-SiMe3-2-S)3)] and CH 3MgCl/C2H5MgCl, individually. EPR, SQUID studies as well as DFT computations Reveal that the NiIII in 1 has a low-spin d7 electronic configuration in a distorted trigonal bipyramidal ligand field. The Ni-C bond lengths of 1.994(3) å in 1 and 2.015(3) å in 2 are comparable to that in the NiIII-methyl state of MCR (̃2.04 å) (Sarangi, R.; Dey, M.; Ragsdale, S. W. Biochemistry 2009, 48, 3146). Under a CO atmosphere, CO triggers homolytic cleavage of the NiIII-CH3 bond in 1 to produce Ni II-thiolate carbonyl [PPN][NiII(CO)(P(C6H 3-3-SiMe3-2-S)3)] (3). Additionally, protonation of 1 with phenylthiol generates NiIII-thiolate [PPN][NiIII(SPh)-(P(C6H3-3-SiMe 3-2-S)3)] (4).
AB - Mononuclear, distorted trigonal bipyramidal [PPN][NiIII(R)- (P(C6H3-3-SiMe3-2-S)3)] (R) Me (1); R) =Et (2)) were prepared by reaction of [PPN][NiIIICl(P(C 6H3-3-SiMe3-2-S)3)] and CH 3MgCl/C2H5MgCl, individually. EPR, SQUID studies as well as DFT computations Reveal that the NiIII in 1 has a low-spin d7 electronic configuration in a distorted trigonal bipyramidal ligand field. The Ni-C bond lengths of 1.994(3) å in 1 and 2.015(3) å in 2 are comparable to that in the NiIII-methyl state of MCR (̃2.04 å) (Sarangi, R.; Dey, M.; Ragsdale, S. W. Biochemistry 2009, 48, 3146). Under a CO atmosphere, CO triggers homolytic cleavage of the NiIII-CH3 bond in 1 to produce Ni II-thiolate carbonyl [PPN][NiII(CO)(P(C6H 3-3-SiMe3-2-S)3)] (3). Additionally, protonation of 1 with phenylthiol generates NiIII-thiolate [PPN][NiIII(SPh)-(P(C6H3-3-SiMe 3-2-S)3)] (4).
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U2 - 10.1021/ja102430d
DO - 10.1021/ja102430d
M3 - Article
C2 - 20568755
AN - SCOPUS:77955816647
VL - 132
SP - 9256
EP - 9258
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 27
ER -