Separation and Optical Resolution of a Pair of atrop Diastereomers of the Octahedral Rhodium(III) Complex with a Nine-Membered S,S-Chelate Ring

Abstract

Treatment of fac-[Rh(aet) 3] (aet = 2-aminoethanethiolate) with 2,2'-bis(bromomethyl)-1,1'-biphenyl gave a mononuclear rhodium(III) complex with a nine-membered S, S-chelate ring, fac-[Rh(aet)(L)] (2+) ([ 1] (2+), L = 2,2'-bis(2-aminoethylthiomethyl)-1,1'-biphenyl). Complex [ 1] (2+) afforded a pair of atrop diastereomers, Delta SS( S ax)/Lambda RR( R ax)-[ 1] (2+) ([ 1a] (2+)) and Delta SS( R ax)/Lambda RR( S ax)-[ 1] (2+) ([ 1b] (2+)), which involves the axial chirality ( R ax/ S ax) about a biphenyl moiety of L, besides the central chirality (Delta/Lambda) about a Rh (III) ion bound by two asymmetric ( R/ S) thioether donors. The atrop diastereomers ([ 1a] (2+) and [ 1b] (2+)) were successfully separated, isolated, and optically resolved, and the circular dichroism (CD) contribution from the axial chirality was evaluated by CD spectral analyses.

Structurally Precise Silver Sulfide Nanoclusters Protected by Rhodium(III) Octahedra with Aminothiolates

“…[20][21][22][23][24][25][26][27][28] One example is the reaction of [Rh(aet) 3 ]w ith Ag + in water, which forms an S-bridged Ag I 3 Rh III 2 pentanuclear complex, [Ag 3 -{Rh(aet) 3 } 2 ] 3+ ,w hich retains the molecular structure of [Rh-(aet) 3 ]. [20][21][22][23][24][25][26][27][28] One example is the reaction of [Rh(aet) 3 ]w ith Ag + in water, which forms an S-bridged Ag I 3 Rh III 2 pentanuclear complex, [Ag 3 -{Rh(aet) 3 } 2 ] 3+ ,w hich retains the molecular structure of [Rh-(aet) 3 ].…”

“…Previously,w es howed that the octahedral rhodium(III) complex [Rh(aet) 3 ](aet = 2-aminoethanethiolate) can bind to transition-metal ions through facially arranged thiolato groups,thereby producing avariety of S-bridged multinuclear and supramolecular coordination compounds. [20][21][22][23][24][25][26][27][28] One example is the reaction of [Rh(aet) 3 ]w ith Ag + in water, which forms an S-bridged Ag I 3 Rh III 2 pentanuclear complex, [Ag 3 -{Rh(aet) 3 } 2 ] 3+ ,w hich retains the molecular structure of [Rh-(aet) 3 ]. [23] Since [Ag 3 {Rh(aet) 3 } 2 ] 3+ is obtained as ar acemic compound consisting of DD and LL isomers,inwhich the two [Rh(aet) 3 ]u nits have the same chiral configuration (D or L), [23] herein, we treated ay ellow aqueous solution of [Ag 3 {Rh(aet) 3 } 2 ](BF 4 ) 3 with d-penicillamine to isolate optically active species.F rom this reaction, we obtained av ery small amount of 1' as adeep-red crystalline solid.…”

Synthesis and crystallographic characterization of a mononuclear cobalt(III) complex possessing both thiolate and thioether donors: reactivity of an thiolate-bridged pentanuclear Co2Ag3 complex with iodomethane

“…In the course of our continuing study of the alkylation reaction of metal complexes with aminothiolate ligands (Okamoto et al, 1999;Chikamoto et al, 2005Chikamoto et al, , 2007Yoshinari & Konno, 2008, 2009, we herein report that an S-bridged Ag I 3 Co III 2 pentanuclear complex, {Ag 3 [Co(L)] 2 } 3+ [L 3-= N(CH 2 NHCH 2 CH 2 S À ) 3 ] (Tokuda et al, 2000), in which two tris(thiolate)-type octahedrally shaped Co III moieties with an aet derivative ligand, [Co(L)], are linearly linked by three Ag I ions, reacts with iodomethane to give a mono(thiolate)bis(thioether)-type complex, [Co(LMe 2 )] 2+ [LMe 2 À = N(CH 2 NHCH 2 CH 2 S À )(CH 2 NHCH 2 CH 2 SCH 3 ) 2 ]. It is noteworthy that the complex was crystallized as a hexafluoridophosphate salt, [Co(LMe 2 )](PF 6 ) 2 , and its molecular structure was fully determined by single-crystal X-ray diffraction analysis.…”

5,7-Dihydrodibenzo[c,e]thiepine

“…As a part of our ongoing studies on the synthesis and structures of the transition metal complexes with thioether donor groups, we prepared a pair of atrop diastereomeric Rh III complexes having a 2,2′-bis(2-aminoethylthiomethyl)-1,1′-biphenyl ligand (Yoshinari & Konno, 2008). We report herein the structure of the title compound, 5,7-dihydrodibenzo[c,e]thiepine, (I), which was accidentally obtained in the course of a direct synthesis of 2,2′-bis(2-aminoethylthiomethyl)-1,1′-biphenyl from 2,2′-bis(bromomethyl)-1,1′-biphenyl and 2-aminoethanethiol.…”