Assemblies of multiply bonded [Re2]n+ cores possessing bond orders of 3 or 3.5 that are linked by dicarboxylate bridges

Abstract

An earlier study describing the exchange of the µ-acetato ligands of Re 2 (µ-O 2 CCH 3 )Cl 4 (µ-dppm) 2 (1) and cis-Re 2 (µ-O 2 CCH 3 ) 2 Cl 2 (µ-dppm) 2 (2) by dicarboxylic acids has been expanded to include reactions with the monocarboxylic acid isonicotinic acid, and the dicarboxylic acids adipic acid, 4,4Ј-biphenyldicarboxylic acid, fumaric acid, trans-1,4-cyclohexanedicarboxylic acid and 1,1Ј-ferrocenedicarboxylic acid. Further examples of complexes that are "dimers-of-dimers" and triangular supramolecular assemblies involving retention of the basic electronic and molecular structures of the dirhenium units present in 1 and 2 have been obtained. In addition, the dirhenium complexes Re 2 (µ-O 2 CC 6 H 4 N)Cl 4 (µ-dppm) 2 (7) and cis-Re 2 (µ-O 2 C 6 H 10 CO 2 Et) 2 Cl 2 (µ-dppm) 2 (11) have been isolated, as well as the trimetallic complex cis-Re 2 Cl 2 (µ-dppm) 2 [(µ-O 2 CC 5 H 4 ) 2 Fe] ( 14) that is formed from the reaction of 2 with (C 5 H 4 CO 2 H) 2 Fe. The crystal structures of 7, 11 and 14 are reported.

Synthesis, structure and spectral properties of dithiocarbamato bridged dirhenium(III,II) complexes: A combined experimental and theoretical study

“…The Re-Re distance in 4(L Et )ÁC 2-H 5 OH falls within the range of the corresponding distances in other structurally characterized edge-shared bioctahedral dirhenium complexes [19]. The two Re-P bond lengths ($2.41 Å) in 4(L Et )ÁC 2-H 5 OH are slightly shorter than that observed in other structurally characterized dppm containing Re 2 5+ complexes [3][4][5]. The average…”

“…The reaction of 1 with isonicotinic acid affords the expected dirhenium(III,II) complex Re 2 (l-O 2 CC 5 H 4 N)Cl 4 (l-dppm) 2 [3] whereas with terephthalic acid the centrosymmetric ''dimer-of-dimers'' l-terephthalate complex [(l-dppm) 2 Cl 4 Re 2 ] 2 (l-O 2 CC 6 H 4 CO 2 ) [4] is formed. Similar dicarboxylate-bridged complexes are isolated with the use of adipic acid, fumaric acid and 4,4 0 -biphenyldicarboxylic acid [3]. When trans-1,4-cyclohexanedicarboxylic acid is used the reduced Re 2 4+ complex cis-Re 2 (l-O 2 CC 6 H 10 CO 2 Et) 2 Cl 2 (ldppm) 2 was obtained [3].…”

“…Similar dicarboxylate-bridged complexes are isolated with the use of adipic acid, fumaric acid and 4,4 0 -biphenyldicarboxylic acid [3]. When trans-1,4-cyclohexanedicarboxylic acid is used the reduced Re 2 4+ complex cis-Re 2 (l-O 2 CC 6 H 10 CO 2 Et) 2 Cl 2 (ldppm) 2 was obtained [3]. On the other hand the reactions of 1 with tetrafluoro terephthalic acid and 1,1 0 -ferrocene dicarboxylic acid afford the known Re 2 Cl 4 (l-dppm) 3 complex [3].…”

“…When trans-1,4-cyclohexanedicarboxylic acid is used the reduced Re 2 4+ complex cis-Re 2 (l-O 2 CC 6 H 10 CO 2 Et) 2 Cl 2 (ldppm) 2 was obtained [3]. On the other hand the reactions of 1 with tetrafluoro terephthalic acid and 1,1 0 -ferrocene dicarboxylic acid afford the known Re 2 Cl 4 (l-dppm) 3 complex [3]. When 1 is made to react with acetylene dicarboxylic acid the paramagnetic lalkyne complex Re 2 (l-Cl)(l-g 2 -HCCH)Cl 4 (l-dppm) 2 [5] is formed whereas when 2-butynoic acid is used the diamagnetic l-carbyne complex Re 2 (l-Cl)(l-CCH 2 CH 3 )Cl 4 (l-dppm) 2 [5] is isolated by decarboxylation method.…”

New diruthenium complexes formed via modification with 1,1′-ferrocene dicarboxylic acid

“…Other dimetallic and polymetallic examples include a quadruply bonded Re 2 with 1,1 0 -ferrocene dicarboxylate in a tetradentate chelating mode [32], a dimer of Os 3 clusters bridged by 1,1 0 -ferrocene dicarboxylate [33] and a square tetramer of Pt 4 units bridged by four 1,1 0 -ferrocene dicarboxylate [34]. Reported in this contribution are the isolation and characterization of products from the reactions between 1,1 0 -ferrocene dicarboxylic acid and the Ru 2 (DArF) 3 (OAc)Cl and Ru 2 (DArF) 2 (OAc) 2 Cl type synthons developed by several laboratories including ours [35][36][37][38][39][40][41][42][43].…”