3-Aminopropanethiol versus 2-Aminoethanethiol Leading to Different S-bridged Multinuclear Structures Composed of Rhodium(III) Octahedrons

Abstract

The reactions of fac- [Rh(apt) Design and creation of heterometallic multinuclear complexes have long been one of the most important subjects in synthetic coordination chemistry.1 For this purpose, we have developed a metalloligand approach, in which pre-designed metal complexes with several donor sites are used as a ligand (metalloligand) instead of organic and inorganic ligands, focused on thiolato metal complexes.2 Previously, we showed that fac-[M(aminothiolato-N,S) 3 ]-type complexes act as an Sdonating metalloligand by using three thiolato groups, constructing a variety of S-bridged multinuclear structures that are largely dependent on the coordination geometries of reacting metal ions. hexanuclear complexes, respectively, the structures of which are entirely different from those derived from fac-[Rh(aet) 3 ] (Scheme 1b). To our knowledge, this is the first report that shows the drastic structural change of multinuclear structures, which is induced only by the slight change in chelate-ring sizes.A yellow powder of fac-[Rh(apt) 3 ] ([1]) was prepared from RhCl 3 ¢3H 2 O, 3-aminopropanethiol hydrochloride (Hapt¢HCl), and NaOH in water, according to a modified procedure described in the literature.8,9 Fortunately, we were able to isolate single crystals of [1] from the filtrate after removing the powder by filtration. X-ray diffraction study established that [1] has an expected mononuclear structure in fac-[Rh(apt) 3 ], in which the Rh III center is chelated by three apt ligands in an octahedral geometry, such that three thiolato donors occupy a facial position (Figure 1; av. RhN = 2.16 ¡, RhS = 2.344 ¡, N RhN = 87.2°, SRhS = 92.1°, NRhS(chelate) = 89.9°). 10Complex [1] crystallizes in a chiral space group of R3 and only the ª isomer was observed in the crystal packing. The presence of both the ¦ and ª isomers in a 1:1 ratio in the balk sample of [1] was confirmed by its silent CD spectrum.

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

“…Previously, we showed 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 a variety of S‐bridged multinuclear and supramolecular coordination compounds . One example is the reaction of [Rh(aet) 3 ] with Ag + in water, which forms an S‐bridged Ag I 3 Rh III 2 pentanuclear complex, [Ag 3 {Rh(aet) 3 } 2 ] 3+ , which 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 ]. [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.…”

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

“…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.…”

Jahn–Teller Switching of a Redox-Active Nickel(III) Center in a Homoleptic Thiolato Metalloligand Environment

“…In the course of our long-standing program of using thiolato metal complexes as S-donating metalloligands in multinuclear cluster assemblies, , we recently reported the S-bridged trinuclear complex, [Ni­{Rh­(apt) 3 } 2 ] 3+ ([ 1 Rh ] 3+ ; apt = 3-aminopropanethiolate), where fac -[Rh­(apt) 3 ] acts as a tripodal S-donating metalloligand to nickel. − In [ 1 Rh ] 3+ , the nickel center adopts a Jahn–Teller distorted octahedral geometry with a +III oxidation state, which is reversibly oxidized and reduced to form nickel centers with +IV and +II oxidation states, respectively. Notably, all of the three species are stable enough to be isolated as single crystals, whose structures were established by X-ray analysis.…”