Theoretical studies on the mechanism of the tropo-inversion of the BIPHEP-RuCl2/DPEN complex using the ONIOM method

被引：25

作者：

Yamanaka, M ^{[1
]}

Mikami, K ^{[1
]}

机构：

[1] Tokyo Inst Technol, Dept Appl Chem, Tokyo 1528552, Japan

来源：

ORGANOMETALLICS | 2002年 / 21卷 / 26期

关键词：

D O I：

10.1021/om020215c

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The mechanism of tropo-inversion of the Ru(II) complex bearing a chirally flexible biphenylphosphine (BIPHEP) ligand has been studied by the B3LYP and the ONIOM(B3LYP: HF) methods. The relative energy difference between the favorable (S)I(SS) and the less favorable (R)I(SS) pairs of BIPHEP-RuCl2/DPEN complexes is well comparable to the experimental results. The tropo-inversion of the (S)I(SS) pair to the (R)I(SS) pair is found to be achieved by solvent-assisted rotation around the biphenyl single bond and subsequent recoordination of phosphine to the Ru center. The sterically demanding phenyl groups attached to phosphorus atoms in the BIPHEP-RuCl2 moiety prevented the internal rotation without dissociation of P-Ru coordination.

引用

页码：5847 / 5851

页数：5

共 50 条

[1] ENERGY-ADJUSTED ABINITIO PSEUDOPOTENTIALS FOR THE 2ND AND 3RD ROW TRANSITION-ELEMENTS [J].

ANDRAE, D ;

HAUSSERMANN, U ;

DOLG, M ;

STOLL, H ;

PREUSS, H .

THEORETICA CHIMICA ACTA, 1990, 77 (02) :123-141

[2]

[Anonymous], 1993, HDB ENANTIOSELECTIVE

[3]

Balsells J, 2000, ANGEW CHEM INT EDIT, V39, P3428, DOI 10.1002/1521-3773(20001002)39:19<3428::AID-ANIE3428>3.3.CO

[4]

2-M

[5] The use of achiral ligands to convey asymmetry: Chiral environment amplification [J].

Balsells, J ;

Walsh, PJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (08) :1802-1803

[6] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[7] Asymmetric catalysis with the normally unresolvable, conformationally dynamic 2,2′-bis(diphenylphosphino)-1,1′-biphenyl (biphep) [J].

Becker, JJ ;

White, PS ;

Gagné, MR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (38) :9478-9479

[8] STERIC EFFECTS - A STUDY OF A RATIONALLY DESIGNED SYSTEM [J].

BOTT, G ;

FIELD, LD ;

STERNHELL, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (17) :5618-5626

[9] A new ONIOM implementation in Gaussian98.: Part I.: The calculation of energies, gradients, vibrational frequencies and electric field derivatives [J].

Dapprich, S ;

Komáromi, I ;

Byun, KS ;

Morokuma, K ;

Frisch, MJ .

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, 1999, 461 :1-21

[10] The activation barrier to axial torsion in 2,2'-bis(diphenylphosphino)biphenyl [J].

Desponds, O ;

Schlosser, M .

TETRAHEDRON LETTERS, 1996, 37 (01) :47-48

← 1 2 3 4 5 →