Ligand-coupling assembly of Re(i)-thiolate complexes

Abstract

By taking advantage of solvothermal reactions of Re2(CO)10 with 2-mercaptobenzothiazol (HNS2) or 2-mercaptobenzoxazol (HNOS), a series of Re(I) complexes (1-4) with in situ ligands were synthesized and structurally characterized by X-ray diffraction. In this study, we examined the effects of reaction conditions (i.e., reaction solvents and temperatures) on the HNS2 system to give complexes 1-3, and also compared the reaction products of the HNS2 (2) and HNOS (4) systems under similar reaction conditions. For the HNS2 system, the reaction temperatures at 140 and 120 °C in mesitylene led to different ligands in complexes 1 and 2, respectively. However, at the same temperature of 140 °C, different solvents (mesitylene or benzene) caused the formation of complexes 1 and 3 containing different ligands, respectively. Although the same temperature and solvent were used, HNS2 and HNOS underwent a similar in situ ligand reaction in dinuclear complexes 2 and 4, which surprisingly show both anti and syn conformations, respectively.

Molecular ReI Cages: Structural and Luminescent Properties

“…In our previous studies, a series of Re I complexes, assembled by solvothermal reactions of Re 2 (CO) 10 with 2‐mercaptobenzothiazole or 2‐mercaptobenzoxazole, were synthesized and structurally characterized by X‐ray diffraction. Three in situ ligands involved in coordination with Re I ions were found depending on the reaction conditions (i.e., reaction solvents and temperatures).…”

“…In our previouss tudies, [14] as eries of Re I complexes, assembled by solvothermalr eactions of Re 2 (CO) 10 with 2-mercaptobenzothiazole or 2-mercaptobenzoxazole,w ere synthesized and structurally characterized by X-ray diffraction. Three in situ ligandsi nvolved in coordination with Re I ions were found depending on the reaction conditions (i.e.,r eaction solvents and temperatures).H owever,n ot emperature and solvente ffect on the self-assembly process were observed in this study,a nd this suggestst hat the robust C 3 N 3 S 3 ligand used in the currents ol- vothermal reactions can provideauseful approacht oc onstruct various coordination architectures.…”

“…[12] Solvothermalr eactions can provideg ood opportunities for the generation of new structuralmotifs andlead to the synthesis of functional coordination frameworks and cages. [13] As a part of our continuing interesti nt he design and synthesis of functional metal-containing pyridylthiolates, [14] we report herein that versatile building block [{Re(CO) 4 } 3 (C 3 N 3 S 3 )] (1a) reacts with linear dipyridyl ligands [i.e.,p yrazine( pz), 4,4'-bipyridine (bpy), 1,2-bis(4-pyridyl)ethylene (bpe), bis(4-pyridyl)acetylene (bpa), and 1,4-bis(pyridyl-4-ylethynyl)benzene (bpb)] and at ripyridyl ligand [1,3,5-tris(4-pyridylethynyl)benzene (tpb)] to form as eries of molecular cages [{Re-(CO) 3 } 6 (L) 3 (C 3 N 3 S 3 ) 2 ][ L = pz (2), bpy (3), bpe (4), bpa (5), bpb (6)] and [{Re(CO) 3 } 9 (tpb) 3 (C 3 N 3 S 3 ) 3 ]( 7)u nder solvothermal conditions. Interestingly,v ariouss tructurald imensions and motifs can be systematicallyo btained depending on the different dipyridyl and tripyridyl ligandsu sed in the reaction.…”

Variations in binding modes of 2-mercaptobenzoxazolates in the novel cyclic trinuclear complexes [Mn3(CO)10(μ-SCNOC6H4)3] and [Re3(CO)12(μ-SCNOC6H4)3]

“…The rhenium cluster 2formally results from condensation of three [Re(CO) 4 (  -SCNOC 6 H 4 )] sub-units without secondary carbonyl loss, while 1 can be envisaged to result from initial formation of the manganese analogue, [Mn 3 (CO) 12 (-SCNOC 6 H 4 ) 3 ], followed by subsequent loss of two carbonyls. While this manuscript was in preparation, Tzeng and co-workers reported the solvothermal reaction of [Re 2 (CO) 10 ] with 2-mercaptobenzoxazol gave syn-[Re 2 (CO) 6 (-S 2 CNOC 6 H 4 )] 2 in 55% yield[16], resulting from the formal insertion of sulfur into an N,Sbridged 2-mercaptobenzoxazolate ligand. This insertion and the rhenium to CO ratio of 1:3…”