共查询到20条相似文献,搜索用时 406 毫秒
1.
The observation of homolytic S---CH 3 bond cleavage in (Ph 2P( o-C 6H 4)SCH 3) 2Ni 0 under photochemical conditions has prompted further investigation of nickel(0) complexes and their stability. Tetradentate P 2S′ 2 donor ligands (S′ = thioether type S donor) with aromatic rings incorporated into the P to S links, Ph 2P( o-C 6H 4)S(CH 2) 3S( o-C 6H 4)PPh 2 (arom-PSSP), or the S to S links, Ph 2P(CH 2) 2SCH 2( o-C 6H 4)CH 2S(CH 2) 2PPh 2 (PS-xy-SP), have been used to form four-coordinate, square planar nickel(II) complexes, [(arom-PSSP)Ni](BF 4) 2 (2) and [(PS-xy-SP)Ni](BF 4) 2 (3). The bidentate and tetradentate ligands, Ph 2P( o-C 6H 4)SCH 2CH 3 (arom-PSEt) and Ph 2P(CH 2) 2S(CH 2) 3S(CH 2) 2PPh 2 (PSSP), give similar complexes, [(arom-PSEt) 2Ni](BF 4) 2 (1) and [(PSSP)Ni](BF 4) 2 (4), respectively. Cyclic voltammograms of the Ni 11 complexes in CH 3CN show two reversible redox events assigned to
and
. The one-electron reduction product produced by stoichiometric amounts of Cp 2Co can be characterized by EPR. At 100 K rhombic signals show hyperfine coupling to two phosphorus atoms. Complete bulk chemical reduction of complexes 1, 2, 3 and 4 with Na/Hg amalgam provided the corresponding nickel(0) complexes 1 R, 2 R, 3 R and 4 R which were isolated as red solutions or solids characterized by magnetic resonance properties and reaction products. Photolysis of these nickel(0) complexes leads to S-dealkylation to produce alkyl radicals and dithiolate nickel(II) complexes. Complex 3 crystallized in the monoclinic space group P2t/ c with a=20.740(5), B=9.879(3), C=17.801(4) åA, ß=92.59(2)°, V=3644(2) Å 3 and Z=4; complex 4: P2 1/ c with A=13.815(4), B=13.815(4), C=15.457(5) åA, V=3365.4(14) Å 3 and Z=4. 相似文献
2.
The reaction of dilithiated o-carborane ( closo-1,2-Li 2-1,2-C 2B 10H 10) with CuCl 2 gives 1,1′-bis( o-carborane) (1), 1,3′-bis( o-carborane) (2) and 1,4′-bis( o-carborane) (3). Compound 2 (C 4B 20H 22) crystallizes in the monoclinic space group P2 1/ n with A = 6.9275(6), B = 9.7655(8), C = 12.356(1) Å, β = 90.028(2)° and Z = 2. The structure was solved by direct methods and refined to R = 0.048 and Rw = 0.074. Compound 3 (C 4B 20H 22) crystallizes in the orthorhombic space group P2 12 12 1 with A = 6.8854(5), B = 12.523(1), C = 19.847(1) Å and Z = 4. The structure was solved by direct methods and refined to R = 0.078 and Rw = 0.091. The coupling reaction of dilithiated m-carborane ( closo-1,7-Li 2-1,7-C 2B 10H 10) with CuCl 2 results in the formation of 1,1′-bis( m-carborane) (4) and tetra( m-carborane) (5). 相似文献
3.
The amino-functionalized metallocene (C 5H 4CH(Me)NMe 2) 2ZrCl 2, [(Cp N) 2ZrCl 2] was synthesized by salt metathesis of ZrCl 4 and 2 equiv. of C 5H 4CH(Me)NMe 2Li. The metallocene was obtained in good yield as a mixture of rac and meso diastereomers as established by NMR spectroscopy. The addition of 2 equiv. of n-BuLi to the metallocene (Cp N) 2ZrCl 2 produced a co-catalyst system which was active, at a 1.0 mol% loading, in the dehydropolymerization of PhSiH 3 to poly(phenylsilane), PPSi. The PPSi was obtained as a 9:1 linear–cyclic mixture ( Mw=3850, Mn=2300) as established by GPC analysis; 29Si{ 1H} NMR spectroscopy revealed an atactic polymer microstructure. 相似文献
4.
Reactions of dilithiated diols [HO(CH 2CH 2O) n+1H, n = 1, 2 and 3] with 3,5-bis( N, N-dimethylamino)-1,1-dichlorodicarbaphosphazene (1) in THF have been carried out to afford the first examples of lariat ether type cyclocarbaphosphazene derivatives (C 4H 8O 3PN)(Me 2NCN) 2 (2), (C 6H 12O 4PN)(Me 2NCN) 2 (3) and (C 8H 16O 5PN)(Me 2NCN) 2 (4). Reaction of the tetrasodium salt of pentaerythritol with 1 and bis(morpholino)dichlorodicarbaphosphazene (1a) yielded the first examples of pentaerythritoxy-bridged cyclodicarbaphosphatriazenes [(Me 2NCN) 2PN(OCH 2) 2] 2C (5) and [(OC 4H 8NCN) 2PN(OCH 2) 2] 2C (6). The spectral and structural properties of these compounds are determined and compared with spirocyclic 1,3-propanedioxy derivative of 1 (7) and analogous compounds of cyclophosphazenes. The crystal structures of the compounds 4, 5 and 7 are reported. In addition, complexation studies of compounds 3 and 4 with Na I, K I, Ag I and Cu II ions were carried out by conductance measurements. The studies indicate mostly 1:1 complex formation between the metal ions and lariat ether type cyclocarbaphosphazene derivatives. 相似文献
5.
The triazenide complex of Pt(II) trans-( o-Tol)Pt(PEt 3) 2N 3Ar 2(1) (Ar = p-FC 6H 4) was synthesized by reaction of ( o-Tol)Pt(PEt 3) 2BF 4 with Ar 2N 3Na. The 1H, 19F and 31P NMR spectra of this complex in toluene-d 8 were studied at different temperatures. Two kinds of dynamic processes were observed. The first one is the intramolecular N, N′ migration of the ( o-Tol)Pt(PEt 3) 2 group, detected by 19F NMR. The second process, revealed by 1H, 19P NMR, is the rotation around the partially double N(2)–N(3) bond. Thermodynamic parameters for these processes were calculated from dynamic NMR spectra. 相似文献
6.
Tricarbonyl(η 6-1-oxobenzocyclobutene)chromium(0) (1) can be transformed to tricarbonyl(η 6-1- endo-hydroxybenzocyclobutene) chromium(0) derivatives with substituents R (R=CH 3, CH=CH 2, (CH 2) 4CH=CH 2, (CH 2) 4OSi(Me) 2tBu) at Cl on the exo face of the complex. The relative configuration is proven by an X-ray crystal structure analysis of the trimethylsilyl ether 8 (C 16H 18CrO 4Si: a=8.693(1), b=9.490(1), c=11.063(1) Å, =97.51(1), β=110.32(1), γ=95.38(1)°, triclinic, space group P
(No.2), R=0.037, Rw=0.052 for 4609 observed reflections. Attempts directed at an intramolecular cycloaddition of the ortho-quinodimethane complex derived from 17 by anion promoted ring opening unexpectedly resulted in the formation of 12 as the product of an opening of the proximal bond of the anellated ring located between the hydroxy group and the coordinated aromatic ring in 16. The fact that the intermolecular cycloaddition reaction for 16 is possible in the presence of a dienophile is taken as evidence for an equilibrium between the alcoholate 17 and the two ring opened products 16 and 18. The proximal ring opening of 6 is not observed when the free organic ligand 21 is used as the educt. Ketone complexes 1 and 25 undergo proximal ring opening reaction when treated with alcoholate or primary amines. 相似文献
7.
The reaction of [Re(NMe)Cl 3(PPh 3) 2] with the pentadentate [N 3S 2] ligand pyN 2H 2S 2---H 2 [2,6-bis(2-mercaptophenylamino)dimethylpyridine] (1) in the presence of triethylamine did not yield the anticipated six-coordinate complex [Re(NMe)(η 5-pyN 2HS 2)] (2), but rather resulted in cleavage of the Re(V)=NMe bond. A novel six-coordinate Re(IV) [N 3S]/[NS] complex [Re(η 4-SC 6H 4---2-NCH 2---C 5H 3N---C=NC 6H 4---2-S)(η 2-NHC 6H 4---2-S)] (4) was thus obtained with the simultaneous coordination of 2-aminothiophenol, a dianionic bidentate [NS] donor resulting from the decomposition of the parent ligand and ligand 3, a dianionic tetradentate [N 3S] donor formed by partial self-condensation and subsequent oxidation of the parent ligand 1. Crystal data for 4: C 25H 18N 4S 3Re·CH 2Cl 2, monoclinic, space group P2 1/ n, a=9.255(2) Å, b=11.181(2) Å, c=25.316(4) Å, β=97.434(3)°, V=2587.8(7) Å 3 and Z=4. 相似文献
8.
The thermal and photochemical reactions of CpRe(PPh 3) 2H 4 and CpRe(PPh 3)H 4 (Cp = η5-C 5H 5) with PMe 3, P( p-tolyl) 3, PMe 2Ph, DMPE, DPPE, DPPM, CO, 2,6-xylylisocyanide and ethylene have been examined. While CpRe(PPh 3) 2H 2 is thermally inert, it will undergo photochemical substitution of one or two PPh 3 ligands. With ethylene, substitution is followed by insertion of the olefin into the C-H bond of benzene, giving ethylbenzene. CpRe(PPh 3)H 4 undergoes thermal loss of PPh 3, which leads to substituted products of the type CpRe(L) H 4. Photochemically, reductive elimination of dihydrogen occurs preferentially. The complex trans-CpRe(DMPE)H 2 was structurally characterized, crystallizing in the monoclinic space group P2 1/ n (No. 14) with a = 6.249(6), b = 16.671(8), c = 13.867(7) Å, β = 92.11(6)°, V = 1443.7(2.9) Å and Z = 4. The complex trans-CpRe(PMe 2Ph) 2H 2 was structurally characterized, crystallizing in the monoclinic space group P2 1/ n (No. 14) with a = 7.467(3), b = 23.874(14), c = 11.798(6) Å, β = 100.16(4)°, V = 2070.2(3.4) Å 3 and Z = 4. 相似文献
9.
The reactivity, towards nucleophiles and electrophiles, of dimolybdenum allenylidene complexes of the type [Cp 2Mo 2(CO) 4(μ,η 2(4e)-C=C=CR1R2)] (Cp=η 5-C 5H 5) has been investigated. The nucleophilic attacks occur at the C γ carbon atom, while electrophiles affec the C atom. Variable temperature solution 1H NMR studies show a dynamic behavior of these complexes consisting of an equilibrium between two enantiomers with a symmetrical [Cp 2Mo 2(CO) 4(μ-σ,σ(2e)-C=C=CR1R2)] transition state. Extended Hückel MO calculations have been carried out on the model [Cp 2Mo 2(CO) 4(μ,η 2-C=C=CH 2]. The calculated charges of the allenylidene carbon atoms suggest that the electrophilic attacks are under charge control, while the nucleophilic attacks are rather under orbital control. 相似文献
10.
Cp #2Yb (Cp #=C 5H 4(CH 2) 2NMe 2) has been obtained by reaction of YbI 2(THF) 2 with 2 equiv. of C 5H 4(CH 2CH 2NMe 2)K in THF. The X-ray structure analysis shows a bent structure with intramolecular coordination of both nitrogen atoms to ytterbium. The reaction of C 60-fullerene with Cp #2Yb leads to the formation of the fullerenide derivative [Cp #2Yb] 2C 60, which shows an ESR signal in the solid state and in THF solution at room temperature (solid: Δ H = 50 G, G = 1.9992; solution: Δ H = 10 G, G = 2.0001) and a magnetic moment of 3.6 BM. The lutetium fullerenides CpLu(C 60)(DME) (3) and Cp *Lu(C 60)(DME)(C 6H 5CH 3) (4), (Cp = η 5−C 5H 5, Cp * = η 5−C 5Me 5), were obtained by reaction of C 60 with CpLu(C 10H 8) (DME) and Cp *Lu(C 10H 8) (DME) in toluene. Both complexes are paramagnetic (μ eff = 1.4 and 0.9 BM) and exhibit temperature-dependent ESR signals (293 K: g = 1.992 and 2.0002 respectively). 相似文献
11.
Lithiation of [ p-Bu t-calix[4]-(OMe) 2(OH) 2] (1), followed by reaction with TiCl 3(thf) 3 or TiCl 4(thf) 2, led to the corresponding titanium-calix[4]arene complexes [ p-Bu t-calix[4]-(OMe) 2(O) 2]TiCl] (2) and [ p-Bu t-calix[4]-(OMe) 2(O) 2]TiCl 2] (3), respectively. Reaction of 1 with TiCl 4(thf) 2 results in demethylation of the calix[4]arene and the obtention of [ p-Bu t-calix[4]-(OMe) 2(O) 3]TiCl] (4), whose hydrolysis led to [ p-Bu t-calix[4]-(OMe)(OH) 3] (6). The preparation of 6 can be carried out as a one-pot synthesis. Both 2 and 4 undergo alkylation reactions using conventional procedures, thus forming surprisingly stable organometallic species, namely [ p-Bu t-calix[4]-(OMe) 2(O) 2Ti(R)] (R = Me (7); CH 2Ph (8), p-MeC 6H 4 (9) and [ p-Bu t-calix[4]-(OMe)(O) 3Ti(R)] (R = Me (10); CH 2Ph (11); p-MeC 6H 4 (12)). Complexes 7 and 9 undergo a thermal oxidative conversion into 10 and 12, occurring with the demethylation of one of the methoxy groups. A solid state structural property of 9 and 12 has been revealed by X-ray analysis showing a self-assembly of the monomeric units into a columnar polymer, where the p-tolyl substituent at the metal functions as a guest group for an adjacent titanium-calixarene. Reductive alkylation of 3 with Mg(CH 2Ph) 2 gave 8 instead of forming the corresponding dialkyl derivative. Two synthetic routes have been devised for the synthesis of the Ti(III)-Ti(III) dimer [ p-Bu t-calix[4]-(OMe)(O) 3Ti] 2] (13): the reduction of 4 and the reaction of TiCl 3(thf) 3 with the lithiated form of 6. A very strong antiferromagnetic coupling is responsible for the peculiar magnetic behavior of 13. The proposed structures have been supported by the X-ray analyses of 4, 9, 12 and 13. 相似文献
12.
1,10-Phenanthroline-5,6-dione (C 12H 6N 2O 2 (1)) reacts with V(η 6-mesitylene) 2 and Ti(η 6-toluene) 2 affording coordination compounds of general formula M( O, O′---C 12H 6N 2O 2) 3 (M=Ti (2); M=V (3)) which further react with TiCl 4 or TiCp 2(CO) 2 yielding the tetrametallic species M( O, O′---C 12H 6N 2O 2--- N, N′) 3(M′L n) 3 (M=V, M′L n=TiCl 4 (4); M=Ti, M′L n=TiCp 2 (5); M=V, M′L n=TiCp 2 (6)). The complex salt [Fe( N, N′---C 12H 6N 2O 2) 3][PF 6] 2 (7) has been obtained from iron(II) chloride tetrahydrate and 1 in the presence of NH 4PF 6. The reaction of 7 with TiCp 2(CO) 2 affords the tetrametallic derivative [Fe( N, N′---C 12H 6N 2O 2--- O, O′) 3(TiCp 2) 3][PF 6] 2 (8). TiCl 2(THF) 2 reacts with MCp 2( O, O′---C 12H 6N 2O 2) to give MCp 2( O, O′---C 12H 6N 2O 2--- N, N′)TiCl 2 (M=Ti (9); M=V (10)). By reaction of TiCp 2( O, O′---C 12H 6N 2O 2--- N, N′)TiCl 2 (9) with C 12H 6N 2O 2, the bimetallic derivative TiCp 2( O, O′---C 12H 6N 2O 2--- N, N′)TiCl 2( O, O′---C 12H 6N 2O 2) (11) has been prepared, which readily adds to TiCl 4, to give the trimetallic titanium derivative TiCp 2( O, O′---C 12H 6N 2O 2--- N, N′)TiCl 2( O, O′---C 12H 6N 2O 2--- N, N′)TiCl 4 (12). VCp 2( O, O′---C 12H 6N 2O 2--- N, N′)TiCl 2 (10) reacts with the tris-chelate iron(II) cation 7 affording the heptametallic cationic complex [Fe( N, N′---C 12H 6N 2O 2--- O, O′)TiCl 2( N, N′---C 12H 6N 2O 2--- O, O′)VCp 2] 3 +2 isolated as the hexafluorophosphate 13. 相似文献
13.
The molecular structure of trans-[Pd(PhC(O)CHP(n-C 4H 9) 3) 2Cl 2] has been determined via a single crystal X-ray diffraction study: triclinic, P1, a = 8.876(2), b = 10.908(3), c = 11.938(4)Å, = 97.06(2)°, β = 102.79(2)°, γ = 100.51(2)°, V= 1092.1(5)Å 3, Z = 1 and R( F) = 4.61%. The phosphorus ylide molecules are bound to the palladium atom through their methine carbon atoms, the overall coordination geometry about the palladium being square planar. The protons in the ortho-positions of the two phenyl group are poised above and below the palladium atom, suggesting that the complex is a precursor of the ortho-metalated complex [Pd(μ-Cl)(C 6H 4C(O)CHP(n-C 4H 9) 3)] 2 synthesized earlier in our laboratory. 相似文献
14.
Treatment of the A-ring aromatic steroids estrone 3-methyl ether and β-estradiol 3, 17-dimethyl ether with Mn(CO) 5+BF 4− in CH 2Cl 2 yields the corresponding [(steroid)Mn(CO) 3]BF 4 salts 1 and 2 as mixtures of and β isomers. The X-ray structure of [(estrone 3-methyl ether)Mn(CO) 3]BF 4 · CH 2Cl 2 (1) having the Mn(CO) 3 moiety on the side of the steroid is reported: space group P2 1 with a=10.3958(9), b=10.9020(6), c=12.6848(9) Å, β=111.857(6)°, Z=2, V=1334.3(2) Å 3, calc=.481 cm −3, R=0.0508, and wR=0.0635. The molecule has the traditional ‘piano stool’ structure with a planar arene ring and linear Mn---C---O linkages. The nucleophiles NaBH 4 and LiCH 2C(O)CMe 3 add to [(β-estradiol 3,17-dimethyl ether)Mn(CO) 3]BF 4 (2) in high yield to give the corresponding - and β-cyclohexadienyl manganese tricarbonyl complexes (3). The nucleophiles add meta to the arene -OMe substituent and exo to the metal. The and β isomers of 3 were separated by fractional crystallization and the X-ray structure of the β isomer with an exo-CH 2C(O)CMe 3 substituent is reported (complex 4): space group P2 12 12 1 with a=7.5154(8), b=15.160(2), c=25.230(3) Å, Z=4, V=2874.4(5) Å 3, calc=1.244 g cm −3, R=0.0529 and wR2=0.1176. The molecule 4 has a planar set of dienyl carbon atoms with the saturated C(1) carbon being 0.592 Å out of the plane away from the metal. The results suggest that the manganese-mediated functionalization of aromatic steroids is a viable synthetic procedure with a range of nucleophiles of varying strengths. 相似文献
15.
Three new crystalline tin selenide salts have been prepared from the reactions of [PPh 4] 2[Sn(Se 43] in supercritical solvents. The starting material pyrolyzes in supercritical acetonitrile to form [PPh 4] 4[Sn 6Se 21] (I), and it also reacts with SnSe in supercritical ammonia leading to a mixture of [PPh 4] 4[Sn 3Se 11] 2 (II). and [PPh 4] 2[Sn(Se 4)(Se 6) 2] (III). All three compounds have been characterized by single crystal X-ray diffraction. Crystallographic data: for I, C 96H 90P 4Se 21Sn 6, space group triclinic, P-1, A = 18.763(3), B = 24.600(4), C = 13.137(1) Å, = 102.63(1), β = 93.66(1), γ = 108.72(1)°, V = 5544(1) Å 3, Z = 2, R = 0.0350, RW = 0.0317: for II, C 96H 80P 4Se 22Sn 6, space group monoclinic P2 1/ c, A = 31.500(4), B = 16.572(3), C = 22.352(3) Å, β = 103.53(1)°, V = 11344(3) Å 3, Z = 4, R = 0.0771, RW = 0.0664: for III, C 48H 40P 2Se 16Sn, space group monoclinic, C2/ c, A = 25.381(2), B = 13.934(4), C = 19.465(3) Å, β = 121.587(8)°, V = 5867(2) Å 3, Z = 4, R = 0.0807, RW = 0.0650. One of the compounds, [PPh 4] 2[Sn(Se 4(Se 62], is a molecular cluster while the other two complexes [PPh 4] 4[Sn 3Se 11] 2 and [PPh 4] 4[Sn 6Se 21], are one dimensional tin selenide chains. The structures of the two chains are related and consits of tetrahedral and distorted trigonal bipyramidal tin(IV) centers bridged by Se 2−, Se 22− and Se 32− chains. 相似文献
16.
The reactions of arene–metal complexes (arene = p-cymene, benzene or pentamethylcyclopentadienyl, metal = Ru, Rh or Os), including 1,3,5-triaza-7-phosphatricyclo-[3.3.1.1]decanephosphine (pta) and chloro co-ligands, with 9-methylguanine, adenine, and a series of nucleosides were studied in water to ascertain the binding modes. The products were characterized by NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS). Tandem mass spectrometry was found to provide excellent information on preferential binding sites. In general, the N7 position on guanine (the most basic site) was found to be the preferred donor atom for coordination to the metal complexes. The X-ray structures of the precursor complexes, [(η 5-C 10H 15)RhCl(pta-Me) 2]Cl 2, [(η 6-C 10H 14)OsCl(pta) 2]Cl, and [(η 6-C 6H 6)OsCl 2(CH 3CN)], are also reported. 相似文献
17.
Kinetic results are reported for intramolecular PPh 3 substitution reactions of Mo(CO) 2(η 1-L)(PPh 3) 2(SO 2) to form Mo(CO) 2(η 2-L)(PPh 3)(SO 2) (L = DMPE = (Me) 2PC 2H 4P(Me) 2 and dppe=Ph 2PC 2H 4PPh 2) in THF solvent, and for intermolecular SO 2 substitutions in Mo(CO) 3(η 2-L)(η 2-SO 2) (L = 2,2′-bipyridine, dppe) with phosphorus ligands in CH 2Cl 2 solvent. Activation parameters for intramolecular PPh 3 substitution reactions: Δ H≠ values are 12.3 kcal/mol for dmpe and 16.7 kcal/mol for dppe; Δ S≠ values are −30.3 cal/mol K for dmpe and −16.4 cal/mol K for dppe. These results are consistent with an intramolecular associative mechanism. Substitutions of SO 2 in MO(CO) 3(η 2-L)(η 2-SO 2) complexes proceed by both dissociative and associative mechanisms. The facile associative pathways for the reactions are discussed in terms of the ability of SO 2 to accept a pair of electrons from the metal, with its bonding transformations of η 2-SO 2 to η 1-pyramidal SO 2, maintaining a stable 18-e count for the complex in its reaction transition state. The structure of Mo(CO) 2(dmpe)(PPh 3)(SO 2) was determined crystallographically: P2 1/ c, A=9.311(1), B = 16.344(2), C = 18.830(2) Å, ß=91.04(1)°, V=2865.1(7) Å 3, Z=4, R( F)=3.49%. 相似文献
18.
1. 1. The functional terminal oxidase of the light-anaerobically grown Rhodopseudomonas spheroides cells was found to be the o-type cytochrome, whereas that of the dark-aerobically grown cells was the a-type cytochrome. When the dark-aerobically grown cells were further incubated under a semianaerobic condition in the dark, the content of the o-type cytochrome was increased in these cells, while the synthesis of the a-type cytochrome appeared to be repressed. In Rhodospirillum rubrum cells, grown either aerobically in the dark or anaerobically in the light, cytochrome o was the sole functional terminal oxidase. 2. 2. Reactions with the a-type and o-type cytochromes from Rhodopseudomonas spheroides and also with the o-type cytochrome from Rhodospirillum rubrum were compared using reduced yeast cytochrome c as substrate. The reaction with the a-type cytochrome was far less sensitive to NaN3 and hydroxylamine than those with the o-type cytochromes, whereas all the reactions were inhibited by KCN in apparently the same manner.
Abbreviations: Rps, Rhodopseudomonas; Rsp, Rhodospirillum; DCIP, 2,6-dichlorophenol-indophenol 相似文献
19.
Low-temperature photodissociation spectra of membranes from the thermophile PS3 reveal cytochromes o and a3. The latter reacts with O 2 at −103°C to give a light-insensitive compound(s), but the initial stages of O 2 binding to cytochrome o could not be studied under these conditions. Photochemical action spectra identify cytochromes a3 and o, but not a CO-binding c-type cytochrome, as functional terminal oxidases in this bacterium. 相似文献
20.
Sodium salt of a water-soluble, anionic, and monomeric 1:2 complex of Au(I) with a dianion of thiosalicylic acid TSA 2−(Hin2 TSA) = o-HS(C 6H 4)COOH) was first prepared and isolated as colorless needle crystals through a stoichiometric reaction of NaAuCl 4:H 2TSA:NaOH = 1:4:8 molar ratio in aqueous/EtOH solution. In this reaction, TSA 2− ligand has played a role of a reducing agent for the starting Au(III) ion and also of donor ligands coordinating to the reduced Au(I). This compound was characterized by complete elemental analyses, TG/DTA, FT-IR, 2D-NMR ( 1H- 1H COSY, 1H- 13C HMBC, and 1H- 13C HMQC) spectroscopy, and the molmass measurement based on the cryoscopic method. It was shown that this complex was a monomeric species of Au(I) with a formula of Na 3[Au(TSA) 2]·5H 2O in the solid state, but not a polymeric species even in aqueous solution. A full assignment of seven carbon and four proton resonances in the coordinated TSA 2− ligand was achieved by the 2D 1H- 13C HMBC NMR technique. 相似文献
|