933779-29-4Relevant academic research and scientific papers
Synthesis and Reactivity of Multinuclear Gold Complexes with (Diphenylphosphanyl)ferrocene and Oxygen Ligands
Schulz, Ji?í,Císa?ová, Ivana,Gyepes, Róbert,?těpni?ka, Petr
, p. 6992 - 6996 (2021)
AuI complexes combining hard oxygen and soft (diphenylphosphanyl)ferrocene (L) ligands in their molecules were synthesized, viz. the gold hydroxides [Au(OH)(L-κP)] (5) and [{Au(L-κP)}2(μ-OH)][BF4] (4), and the oxonium cluster [{Au(L-κP)}3(μ3-O)][BF4] (1). In-situ auration of 1 produced [{Au(L-κP)}4(μ4-O)][BF4]2 (2), which spontaneously converted into a dimeric tetragold complex featuring bridging phosphanylferrocenyl groups geminally diaurated in position 2 of the ferrocene scaffold. The same complex and its isomer incorporating ferrocene-1,1′-diyl bridges resulted similarly from 4. Upon crystallization, compound 5 underwent a redox reaction, producing a structurally unique, crown-like, mixed-valent Au0/AuI cluster, [Au7(L-κP)6]OH. Compounds 1 and 5 were used to prepare the analogous, N-bridged complexes, [{Au(L-κP)}3(μ3-NFc)][BF4] (Fc=ferrocenyl) and [{Au(L-κP)}4(μ4-N)][BF4]. The compounds were structurally characterized and further studied by DFT calculations.
Auranofin and related heterometallic gold(I)-thiolates as potent inhibitors of methicillin-resistant Staphylococcus aureus bacterial strains
Hokai, Yozane,Jurkowicz, Boruch,Fernández-Gallardo, Jacob,Zakirkhodjaev, Nuruddinkodja,Sanaú, Mercedes,Muth, Theodore R.,Contel, María
, p. 81 - 88 (2014/07/07)
A series of new heterometallic gold(I) thiolates containing ferrocenyl-phoshines were synthesized. Their antimicrobial properties were studied and compared to that of FDA-approved drug, auranofin (Ridaura), prescribed for the treatment of rheumatoid arthritis. MIC in the order of one digit micromolar were found for most of the compounds against Gram-positive bacteria Staphylococcus aureus and CA MRSA strains US300 and US400. Remarkably, auranofin inhibited S. aureus, US300 and US400 in the order of 150-300 nM. This is the first time that the potent inhibitory effect of auranofin on MRSA strains has been described. The effects of a selected heterometallic compound and auranofin were also studied in a non-tumorigenic human embryonic kidney cell line (HEK-293).
Diphenylphosphinoferrocene gold(I) acetylides: Synthesis of heterotri- And heterotetrametallic transition metal complexes
Packheiser, Rico,Jakob, Alexander,Ecorchard, Petra,Walfort, Bernhard,Lang, Heinrich
, p. 1214 - 1226 (2009/01/30)
The synthesis and reaction chemistry of heterobimetallic FcPPh 2AuCl (1) and FcPPh2Au-C≡CR compounds (3a, R = bipy; 3b, R = C6H4-4-C≡N; 3c, R = C5H 4N-4; 3d, R = NCN-H; 3e, R = NCN-I; Fc = (η5-C 5H5)(η5-C5H4)Fe; bipy = 2,2′-bipyridyl-5-yl; NCN = [C6H2(CH 2NMe2)2-2,6]-) toward diverse organometallic molecules is described. In context with this background, 1 was prepared by reacting FcPPh2 with (tht)AuCl (tht = tetrahydrothiophene). The reaction of 1 either with HC≡CR (2a, R = bipy; 2b, R = C6H4-4-C≡N; 2c, R = C5H 4N-4) or with the lithium acetylides LiC≡CR (2d, R = NCN-H; 2e, R = NCN-I) gave complexes 3a-3e in good yield. In 1 the gold(I) chloride entity was further reacted with the organometallic alkyne HC≡CMLn (4a, MLn = (η-C6H5)Cr(CO)3; 4b, MLn = Fc; 4c, MLn = Rc; Rc = (η5-C 5H5)(η5-C5H4)Ru) to afford the heterotrimetallic complexes FcPPh2Au-C≡CML n (5a, MLn = (η6-C6H 5)Cr(CO)3; 5b, MLn = Fc; 5c, MLn = Rc) in which three different transition metal atoms are connected via rigid-rod structured carbon-rich units. Complexes 3a-3e feature with their terminal nitrogen donor groups a further binding site, which allows the introduction of a third metal-containing fragment. In this context, the reaction of 3b with [Ru]N≡N[Ru] (6) ([Ru] = [η3-mer-(2,6-(Me 2NCH2)2C5H3N}-RuCl 2]) resulted in the formation of neutral heterotrimetallic FcPPh 2Au-C≡C-C6H4-4-C≡N-[Ru] (7). The synthesis of an even heterotetrametallic complex [FcPPh2Au-C≡C- C5H4N-Cu {(Me3SiC≡C)2[Ti]}]OTf (9) could be achieved by treatment of 3c with the organometallic π-tweezer {[Ti](μ-σ,π-C≡CSiMe3)2} CuOTf (8a). Heterobimetallic 3a afforded in a straightforward reaction with equimolar amounts of (nbd)Mo(CO)4 (14) (nbd = 1,5-norbornadiene) and {[Ti](μ-σ,π-C≡CSiMe3)2}MX (8b, M = Cu(N≡CMe), X = PF6; 8c, M = Ag, X = OClO3), respectively, compounds FcPPh2Au-C≡C-bipy[Mo(CO)4] (15) and (FcPPh2Au-C≡C-bipy[{[Ti](μ-σ,π- C≡CSiMe3)2}M])X (16a, M = Cu, X = PF6; 16b, M = Ag, X = ClO4). The synthesis of the Fe-Au-Pt NCN pincer molecule FcPPh2Au-C≡C-NCN-Pt-C=CR (13a, R = bipy; 13b, R = C6H4-4-C≡N) was possible by the consecutive reaction of Me3SiC=C-NCN-PtCl (10) with Li-2a or Li-2b to give Me 3SiC≡C-NCN-Pt-C=CR (11a, R = bipy; lib, R = C6H 4-4-C≡N), which with [n-Bu4N]F produced HC≡C-NCN-Pt-C=CR (12a, R = bipy; 12b, R = C6H 4-4-C≡N). On reacting 12a and 12b with 1, complexes 13a and 13b were formed, which are highly insoluble, and hence, no further reactions were carried out. The solid state structures of 3a, 3b, 3e, 5b, 5c, and 16a are reported. Most characteristic for these complexes is that the appropriate transition metals are linked by carbon-rich organic bridging units. The electrochemical properties of selected samples (3a-3c, 5a-5c, 7, 9, 16a, and 16b) are reported. The cyclovoltammetric data show that there is no significant influence of the organic and organometallic acetylide units on the redox potential of the diphenylphosphino ferrocene in 3a- 3c and 5a-5c. Remarkable is that the chelate coordination of the bipyridyl unit to Cu(I) in 16a results in a reduction of Cu(I) followed by reoxidation of Cu(0) without any structural change of the molecule involved, which is unique in titanium(IV)-copper(I) chemistry.
Synthesis, characterization and electrochemical behavior of unsymmetric transition metal-terminated biphenyl ethynyl thiols
R??ler, Katrin,Rüffer, Tobias,Walfort, Bernhard,Packheiser, Rico,Holze, Rudolf,Zharnikov, Michael,Lang, Heinrich
, p. 1530 - 1545 (2007/10/03)
The synthesis of the biphenyl alkynyl thiols and thioesters R′-C{triple bond, long}C-C6H4-C6H4-SR (3: R′ = SiMe3, R = C(O)Me; 4: R′ = SiMe3, R = H; 5: R′ = H, R = C(O)Me) from I-C6H4-C6H4-SC(O)Me (1) is described. Molecules 1 and 5 have been used as starting materials in the synthesis of mono- and heterobimetallic transition metal complexes of type LnM′-C{triple bond, long}C-C6H4-C6H4-SR (7: LnM′ = Fc, R = C(O)Me; 8: LnM′ = Fc, R = H; 10: LnM′ = (Ph3P)Au, R = C(O)Me; 14: LnM′ = FcPPh2-Au, R = C(O)Me; Fc = (η5-C5H5)(η5-C5H4)Fe; FcPPh2 = (η5-C5H5)(η5-C5H4PPh2)Fe). While complex 7is accessible by the Sonogashira cross-coupling of Fc-C{triple bond, long}CH (6) with 1, molecules 10 and 14 can be prepared by treatment of the thioester 5 with (Ph3P)AuCl (9) and FcPPh2-AuCl (13), respectively. The molecular solid state structures of 3, 7, 10 and 13-15 have been determined by single crystal X-ray crystallographic analysis. Typical features of these species are their linear M-C{triple bond, long}C-C6H4-C6H4-SR structure and the lack of coplanarity of the biphenyl arene rings. The overall length of these complexes are 13.345(2) A? for 3 (molecule A), 15.146(3) A? for 7, 15.705(2) A? for 10 (molecule A) and 15.649(4) A? for 14. The thioester groups are pointing away from the ferrocene building block. In 7 a linear 1D chain is set-up by π-interactions between two independent molecules of 7. Characteristic for 15 is the formation of a Au2I2 ring, while 13 is monomeric. All compounds were studied with cyclic voltammetry. Characteristic are the reversible ferrocene Fe(II)/Fe(III) redox wave, the irreversible reduction of Au(I) to Au(0), the oxidative cleavage of the S-C(O)Me sulfur-carbon (3, 5, 7, 10 and 14) and of the sulfur-hydrogen bond (4 and 8), respectively. Electronic effects extending from the -SH-end group to the ferrocene unit resulting in considerable shifts of the redox potential of the latter entity are found. Coordination of Au(I) at the FcPPh2 moiety also results in a shift of the redox potential of the ferrocene group indicative of an electron withdrawing effect of the Au(I) species.
