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1.
Liquid crystalline 4-XC 6H 4N=NC 6H 4X-4′ [X = C 4H 9 (1a), C 1OH 21 (1b), OC 4H 9 (1c), OC 8H 17(1d)] can be easily prepared in high yields from the corresponding anilines. In order to study the influence of metals on the thermal properties of these materials, we have obtained adducts [AuCl 3(4-C 4H 9OC 6H 4N=NC 6H 4OC 4H 9-4′)] (2) and [Ag(OC1O 3)L 2] [L = 4-XC 6H 4N=NC 6H 4X-4′; X = OC 4H, (3a), OC 8H 17 (3b)]. The silver adducts show themotropic behaviour. Mercuriation of dialkylazobenzenes 1a-b takes place with [Hg(OAc) 2] and LiCl to give [Hg(R)Cl] [R = C 6H 3(N=NC 6H 4X-4′)-2, X-5; X = C 4H 9 (bpap) (4a), C 10H 21 (dpap) (4b)] while dialkoxyazobenzenes 1c–d require [Hg (OOCCF 3) 2] to obtain [Hg(R)Cl] [R = C 6H 3(N---NC 6H 4X-4′)-2, X-5; X = OC 4H 9 (bxpap) (4c), OC 8H 17 (4d)]. 4a-c react with NaI to give [HgR 2] [R= bpap (5a), dpap (5b), bxpap (5c), oxpap (5d)l. Both chloroaryl-, 4a and 4c, and diaryl-mercurials, 5a and 5c, act readily as transmetailating agents towards [Me 4N] [AuCl 4] in the presence of [Me 4N]Cl to give [Au(η 2-R)Cl 2] [R = bpap (6a), bxpap (6b)]. After reaction of [AuCl 3(tht)] (tht = tetrahydrothiophene) with [Me 4N]Cl and 4b (1:2:1), [Me 4N][Au(dpap)Cl 3] (7) can be isolated. C---H activati bxpap (8b)]. None of the complexes 4–8 shows mesomorphic behaviour. 相似文献
2.
Reactions of [(η 6-arene)RuCl 2] 2 (1) (η 6-arene= p-cymene (1a), 1,3,5-Me 3C 6H 3 (1b), 1,2,3-Me 3C 6H 3 (1c) 1,2,3,4-Me 4C 6H 2(1d), 1,2,3,5-Me 4C 6H 2 (1e) and C 6Me 6 (1f)) or [Cp*MCl 2] 2 (M=Rh (2), Ir (3); Cp*=C 5Me 5) with 4-isocyanoazobenzene (RNC) and 4,4′-diisocyanoazobenzene (CN–R–NC) gave mononuclear and dinuclear complexes, [(η 6-arene)Ru(CNC 6H 4N=NC 6H 5)Cl 2] (4a–f), [Cp*M(CNC 6H 4N=NC 6H 5)Cl 2] (5: M=Rh; 6: M=Ir) , [{(η 6-arene)RuCl 2} 2{μ-CNC 6H 4N=NC 6H 4NC}] (8a–f) and [(Cp*MCl 2) 2(μ-CNC 6H 4N=NC 6H 4NC)}] (9: M=Rh; 10: M=Ir) , respectively. It was confirmed by X-ray analyses of 4a and 5 that these complexes have trans-forms for the ---N=N--- moieties. Reaction of [Cp*Rh(dppf)(MeCN)](PF 6) 2 (dppf=1,1′-bis (diphenylphosphino)ferrocene) with 4-isocyanoazobenzene gave [Cp*Rh(dppf)(CNC 6H 4N=NC 6H 5)](PF 6) 2 (7), confirmed by X-ray analysis. Complex 8b reacted with Ag(CF 3SO 3), giving a rectangular tetranuclear complex 11b, [{(η 6-1,3,5-Me 3C 6H 3)Ru(μ-Cl} 4(μ-CNC 6H 4N=NC 6H 4NC) 2](CF 3SO 3) 4 bridged by four Cl atoms and two μ-diisocyanoazobenzene ligands. Photochemical reactions of the ruthenium complexes (4 and 8) led to the decomposition of the complexes, whereas those of 5, 7, 9 and 10 underwent a trans-to- cis isomerization. In the electrochemical reactions the reductive waves about −1.50 V for 4 and −1.44 V for 8 are due to the reduction of azo group, [---N=N---]→[---N=N---] 2−. The irreversible oxidative waves at ca. 0.87 V for the 4 and at ca. 0.85 V for 8 came from the oxidation of Ru(II)→Ru(III). 相似文献
3.
The new diphenolato complexes [{Mo(NO){HB(dmpz) 3}Cl} 2Q] where dmpz = 3,5-dimethylpyrazolyl and Q = OC 6H 4(C 6H 4O ( n = 1 or 2), OC 6H 4CR=CRC 6H 4O (R = H or Et), and OC 6H 4CH=CHC 6H 4CH=CHC 6H 4O have been prepared and their electrochemical properties (cyclic and differential pulse voltammetry) compared with previously reported analogues where Q = OC 6H 4O, OC 6H 4EC 6H 4O (E = SO 2, CO and S), OC 6H 4 (CO)C 6H 4 C 6H 4(CO)C 6H 4O and 1,5- and 2,7-O 2C 10H 6. The electrochemical interaction between the redox centres in the new complexes is very weak, in contrast to that in the 1,4-benzenediolato and naphthalendiolato species. The EPR spectra of the reduced mixed-valence species [{Mo(NO){HB(dmpz) 3}Cl} 2Q] − where Q = 1,3- and 1,4-OC 6H 4O and OC 6H 4SC 6H 4O shows that they are valence-trapped at room temperature, whereas those of the dianions [{Mo(NO){HB(dmpz) 3}Cl} 2Q] 2− where Q = 1,4-OC 6H 4O, OC 6H 4EC 6H 4O (E = CO or S) and OC 6H 4CH=CHC 6H 4CH=CHC 6H 4O shows that the unpaired spins on each molybdenum centre are strongly correlated ( J, the spin exchange integral A Mo, the metal-hyperfine coupling constant). The electrochemical properties and the comproportionation constants for the reaction [{Mo(NO){HB(dmpz) 3} Cl} 2Q] + [{Mo(NO){HB(dmpz) 3}Cl}O] 2] 2−2[{Mo(NO) {HB(dmpz) 3}Cl} 2Q] − where Q = diphenolato bridge, are compared with related compounds containing benzenediamido and dianilido bridges. 相似文献
4.
The reaction (1 : 1) between [A
Me 2)Cl 2] and [Hg(2-C 6H 4-N=NPh) 2] gives the complex [(2-PhN=NC 6H 4)A
MeC 2)Cl], which on treatment with AgClO 4 gives [(2-Ph
Me 2)]ClO 4. From this complex, the species [(2-PhN=NC 6H 4)A
Me 2)X] (X = CH 3COO, CN), or [(2-PhN=NC 6H 4)A
Me 2)L] (L = PPh 3, py) are obtained by reaction with the corresponding KX salts or neutral ligands. The crystal structure of [(2-Ph
Me2)][AuCl4] (obtained by metathesis between the corresponding perchlorate and tetramethylammonium salts) has been determined; the cation displays square-planar coordination with two cis-nitrogen (Au---N: 2.166(15), 2.140(14) Å) and two cis-carbon (Au---C: 2.021(16), 2.033(17) Å) atoms bonded to the gold atom. 相似文献
5.
Three tetranuclear clusters [Ru 4H 4(CO) 11(PPh 3)] (1), [Ru 4H 2(CO) 12(PPh 3)] (2) and [Ru 3IrH(CO) 12(PPh 3)] (3) were formed in the reaction of [Ir(CO)Cl(PPh 3) 2] and Na[Ru 3H(CO) 11] in tetrahydrofuran. Complexes 1–3 were characterized by IR and 1H and 31P NMR, and the structure of the clusters was confirmed by single crystal X-ray analysis. In 2 and 3 one of the carbonyls bridges between two ruthenium atoms; otherwise the compounds contain only terminal carbonyls. 相似文献
6.
The structures of HOs 3(CO) 7(PPh 2)(PPh 3)(C 6H 4), HOs 3(CO) 8(PPh 3)(PPh 2C 6H 4) and HOs 3(CO) 7(PPh 2)(PPh 2C 6H 4C 6H 3) are described, the latter illustrating an intracluster reaction of the coordinated benzyne ligand. 相似文献
7.
13C and 31P{ 1H} NMR data at low temperature prompted us to characterize cis-[Rh(CO) 2(PR 3)Cl] (3) (3a, PR 3 = PPh 3; 3b, PR 3 = PMe 2Ph), as surprisingly stable products of the reaction between [{Rh(CO) 2(μ-Cl)} 2] (1) and tertiary phosphines in toluene (P : Rh = 1). Every attempt to isolate solid 3a led to the cis- and trans- halide-bridged dimers [{Rh(CO) 2(μ-Cl)} 2] (5a) and 6a which are formed from 3a by slow decarbonylation, a process which is greatly accelerated by the evaporation of the solvent under vacuum. The analogous reaction of 1 with dimethylphenylphosphine follows a similar pathway; in this case, however, low temperature NMR spectra allowed us to characterize the pentacoordinated dinuclear species [{Rh(CO)2(μ-Cl)}2] (2b) as the unstable intermediate of the bridge-splitting process. The reaction of 3 with a second equivalent of phosphine (P : Rh = 2) leads, at room temperature, to the well known product trans-[Rh(CO)(PR3)2Cl] (8) accompanied by evolution of CO; however our data show that when the reaction is performed at 200 K, decarbonylation is prevented and spectroscopic evidence of trigonal bipyramidal pentacoordinate [Rh(CO)2(PR3)2Cl] (7), stable only at low temperature, can be obtained. 相似文献
8.
The preparation and properties as well as some reactions of a series of arylcarbonylbis(triphenylphosphine)iridium(I) complexes [Ir(Ar)(CO)(PPh 3) 2] (Ar = C 6H 5, C 6F 5, 2-C 6H 4CH 3, 3-C 6H 4CH 3, 4-C 6H 4CH 3, 2-C 6H 4OCH 3, 2,6-C 6H 3-(OCH 3) 2, 4-C 6H 4N(CH 3) 2, 3-C 6H 4Cl, 4-C 6H 4Cl, 4-C 6H 4Cl, 3-C 6H 4CF 3, 4-C 6H 4CF 3) are described, and the most important IR data as well as the 31P NMR parameters of these, without exception trans-planar, compounds are given. Some of the complexes react with molecular oxygen to form well defined dioxygen adducts [Ir(Ar)(O2)(CO)(PPh3)2] (Ar = C6H5, 3-C6H4CH3, 4-C6H4CH3). Complexes with ortho-substituted aryl ligands are not oxygenated. This effect is referred to as a steric shielding of the metal center by the corresponding ortho-substituents. With SO2 the similar irreversible addition compound [Ir(4-C6H4CH3)-(SO2)(CO)(PPh3)2] is obtained. Sulfur dioxide insertion into the Ir---C bond cannot be observed. The first step of the reaction between [Ir(4-C6H4CH3)(CO)(PPh3)2] and hydrogen chloride involves an oxidative addition of HCl to give [Ir(H)(Cl)(4-C6-H4CH3)(CO)(PPh3)2]. Ir---C bond cleavage by reductive elimination of toluene from the primary adduct does not occur except at elevated temperature. 相似文献
9.
Reaction of C 5H 4(SiMe 3) 2 with Mo(CO) 6 yielded [(η 5-C 5H 3(SiMe 3) 2)Mo(CO) 3] 2, which on addition of iodine gave [(η 5-C 5H 3(SiMe 3) 2Mo(CO) 3I]. Carbonyl displacement by a range of ligands: [L = P(OMe) 3, P(OPr i) 3,P(O- o-tol) 3, PMe 3, PMe 2Ph, PMePh 2, PPh 3, P( m-tol) 3] gave the new complexes [(η 5-C 5H 3(SiMe 3) 2 MO(CO) 2(L)I]. For all the trans isomer was the dominant, if not exclusive, isomer formed in the reaction. An NOE spectral analysis of [(η 5-C 5H 3(SiMe 3) 2)Mo(CO) 2(L)I] L = PMe 2Ph, P(OMe) 3] revealed that the L group resided on the sterically uncongested side of the cyclopentadienyl ligand and that the ligand did not access the congested side of the molecule. Quantification of this phenomenon [L = P(OMe) 3] was achieved by means of the vertex angle of overlap methodology. This methodology revealed a steric preference with the trans isomer (less congestion of CO than I with an SiMe 3 group) being the more stable isomer for L = P(OMe) 3. 相似文献
10.
Rhodium(II) complexes with dioximes [Rh(Hdmg) 2(PPh 3)] 2 [I] (Hdmg=monoanion of dimethylglyoxime) and [Rh(Hdmg)(ClZndmg)(PPh 3)] 2 [II] catalyse hydroformylation and hydrogenation reactions of 1-hexene at 1 MPa CO/H 2 and 0.5 MPa H 2 at 353 K, respectively. Hydroformylation with complex [I] produces 94% of aldehydes ( n/ iso=2.2) and 6% 2-hexene whereas the second catalyst [II] gives ca. 40% of aldehydes ( n/ iso=2.1) and 60% of 2-hexene. Corresponding Rh(III) complexes are inactive in hydroformylation except of RhH(Hdmg) 2(PPh 3) [III], which shows activity similar to [I]. Complexes [Rh(Hdmg) 2(PPh 3)] 2 [I], [Rh(Hdmg)(ClZndmg)(PPh 3)] 2 [II], RhH(Hdmg) 2(PPh 3) [III] and [Rh(Hdmg) 2(PPh 3) 2]ClO 4 [V] catalyse 1-hexene hydrogenation with an average TON ca. 18 cycles/mol [Rh]×min. Complex [II] has also been found to catalyse hydrogenation of cyclohexene, 1,3-cyclohexadiene and styrene. 相似文献
11.
The novel alkynyldithiocarboxylate complexes [Fe(η 5-C 5H 5)(S 2CCCR) (dppm-P)] (3a,b) and [Fe(η 5-C 5H 5)(S 2CCCR)(PPh 3)] (4a,b) were obtained through the insertion of CS 2 into the iron-akynyl bond in the complexes [Fe(η 5-C 5H 5)(CCR)(L)(L′] L, L′ = dppm R = Ph (1a), tBu(1b); L = (CO), L′ = (PPh 3) R = Ph (2a), tBu (2b). Variable-temperature 31P{ 1H} NMR studies indicate the presence of two different isomers, [Fe(η 5-C 5H 5)(η 3-S,C,S′---S 2CCCR)(L)(L′)] and [Fe(η 5-C 5H 5(η 2-S,S′-S 2CCCR)(L)(L′)], which rapidly interconvert at room temperature. The synthesis of the precursor complex [Fe(η 5-C 5H 5)(CC tBu)(CO)(PPh 3)] is also described. 相似文献
12.
The aryldiazenido ligands provide the fourth member of the isoelectronic series CO, NO +, RNC, RN 2+ of ligands for transition metal complexes. The first aryldiazenido metal complex was reported in 1964 when p-CH 3OC 6H 4N 2Mo(CO) 2C 5H 5 was prepared by the reaction of NaMo(CO) 3C 5H 5 with p-CH 3OC 6H 4N 2+BF 4−. This review surveys the development of organometallic aryldiazenido chemistry since that time. Such organometallic aryldiazenido derivatives, including RN 2M(CO) 2C 5H 5, RN 2M(CO) 2(Pz 3BH) (M = Cr, Mo, W), [(η 6-Me 6C 6)Cr(CO) 2N 2Ar] +, [(MeC 15H 4)M′(CO) 2N 2Ar] + M′ = Mn, Re), [ trans-PhN 2Fe(CO) 2(PPh 3) 2] +, and PhN 2M′(CO) 2(PPh 3) 2(PPh 3) 2 can be obtained by reactions of arenediazonium salts with suitably chosen transition metal nucleophiles. Analogous methods cannot be used to prepare alkyldiazenido transition metal complexes because of the instability of alkyldiazonium salts. However, the alkyldiazenido derivatives RCH 2N 2M(CO) 2C 5H 5 (R = H or Me 3Si) can be obtained from HM(CO) 3C 5H 5 and the corresponding diazoalkanes. Important aspects of the chemical reactivity of RN 2M(CO) 2Q derivatives (Q = C 5H 5, Pz 3BH) include CO substitution reactions, coordination of the second nitrogen in the RN 2 ligand to give heterobimetallic complexes such as C 5H 5Mo(CO) 2(μ-NNC 6H 4Me)(CO) 2C 5H 5, oxidative addition rections with X 2 X = Cl, Br, I), SnX 4, RSSR, and CINO, and reactions with further RN 2+ to give bis(aryldiazenido) derivatives (RN 2) 2MQL + (L = CO, X −, etc.). Dearylation of an aryldiazenido ligand to a dinitrogen ligand can be effected by reaction of [(MeC 5H 4)M′(CO) 2N 2Ar] + with certain nucleophiles to give (MeC 5H 4)M′(CO) 2N 2. 相似文献
13.
Reaction of R---N=C=N---R (R= p-Me-C 6H 4) and R---P==C=P---R (R=2,4,6- tBu 3C 6H 2) with the di-iron aminocarbene complex [Fe 2(CO) 7{1μ-C(Ph)C(NEt 2)}] (1c) gave corresponding complexes [Fe 2(CO) 6{C(Ph)C(NEt 2)C(NC 6H 4Me)N (C 6H 4Me)}] (2) and [Fe 2(CO) 6{C(Ph)C(NEt 2)C(PC 6H 2tBu 3)P(C 6H 2tBu 3)}] (4), resulting from a coupling reaction with carbon-carbon bond formation. [Fe 2(CO) 5(CNC 6H 4Me){C(Ph)C(NEt 2)N(C 6H 4Me)}], complex 3, obtained in the reaction with R---N=C=N---R, resulted from C=N bond rupture insertion of a nitrene fragment into the Fe=C bond. Complexes 2–4 were characterized by X-ray diffraction. The different geornetries of complexes 2 and 4 are discussed. The formation of these complexes may be explained by cycloaddition on the Fe =C metal-carbene bond. 相似文献
14.
The reaction of K[ReH 6(PPh 3) 2] with [RhCl(CO)L 2] [L= PPh 3, 1,2,5-triphenylphosphole (TPP), or P(OMe) 3] leads to the new electronically unsaturated heterobimetallic polyhydride complexes [(CO)(PPh 3) 2HRe(μ-H) 3RhL 2] in moderate-to-good yields. The structures of these complexes have been established on the basis of spectroscopic data, especially 1H and 31P NMR. The bridging hydride ligands are fluxional but there is either a slow or nonexistent exchange between terminal and bridging hydrides. For L = PPh 3 or TPP, protonation with tetrafluoroboric acid affords quantitatively the cationic complexes [(CO)(PPh 3) 2HRe(μ-H) 3RhHL 2] +, isolated as the BF 4− or the BPh 4− salts. 相似文献
15.
The siloxyanilines o-Me 3SiOC 6H 4NH 2 (1) and p-RMe 2SiOC 6H 4NH 2 (R=H (2); R=Me (3)), and their N-silylated derivatives p-Me 3SiOC 6H 4NHSiMe 3 (4) and p-Me 3SiOC 6H 4N(SiMe 3) 2 (5) have been prepared from ortho- or para-aminophenol and used in the synthesis of imido complexes. Thus, binuclear [{Ti(η 5-C 5H 5)Cl}{μ-NC 6H 4( p-OSiMe 3)}] 2 (6) and mononuclear [TiCl 2{NC 6H 4( p-OSiMe 3)}(py) 3] (7) imido complexes have been obtained from the reaction of 3 and [Ti(η 5-C 5H 5)Cl 3] or [TiCl 2(N tBu)(py) 3], respectively. In contrast, the reaction of 1 with TiCl 4 and tBupy affords the titanocycle [TiCl 2{OC 6H 4( o-NH)---N,O}( tBupy) 2] (8). Compound 5 has also been used to prepare the niobium imide complex [NbCl 3{NC 6H 4( p-OSiMe 3)}(MeCN) 2] (9), by its reaction with NbCl 5 in CH 3CN. These findings have been applied to the synthesis of polynuclear systems. Thus, chlorocarbosilane Si[CH 2CH 2CH 2Si(Me) 2Cl] 4 (CS–Cl) has been functionalized with the ortho- and para-aminophenoxy groups to give 10 and 11, respectively. The use of 11 has allowed the formation of the tetranuclear compound 12. Attempts to synthesize terminal imido titanium complexes from 10 and TiCl 4 in the presence of tBupy and Et 3N, give complex 8 and carbosilane CS–Cl. 相似文献
16.
An S,S′-thioether—thioester chelating ligand [7,8- μ-SCH 2C(O)S-7,8-C 2B 9H 10] − (L 1), incorporating the unit [—(C) 2B 9H 10] − has been synthesized. Reactions have been conducted with RhCl(PPh 3) 3 and PdCl 2(PPh 3) 2 complexes in ethanol. With Rh, L 1 maintains its original cyclic nature and most probably chelation via thioether—thioester takes place. The carborane negative charge may stabilize this original thioether—thioester complex. The other two Rh positions are occupied by two PPh 3 ancillary ligands forming [Rh(L 1)(PPh 3) 2]. The reaction of L 1 with Pd induces ligand modifications and the cyclic nature of L 1 is lost. A transesterification process leading to a dianionic ligand L 2, [7-S-8-SCH 2C(O)OCH 2CH 3−7,8-C 2B 9H 10] 2− has taken place. In this way L 2 is capable of compensating the dipositive Pd charge. The other two Pd positions are occupied by two PPh 3. This reaction has been extended to methanol and isopropanol solvents. The crystal structure of [Pd(L 2)(PPh 3) 2] has been determined. 相似文献
17.
Thermal displacement of coordinated nitriles RCN (R = CH 3, C 2H 5 or n-C 3H 7) in [C 5H 5Fe(L 2)(NCR)]X complexes (L 2 = P(OCH 3) 3) 2, (P(OC 6H 5) 3) 2 or (C 6H 5) 2PC 2H 4P(C 6H 5) 2 (DPPE)) by E(CH 3) 2 affords high yields of [C 5H 5Fe(L 2)(E(CH 3) 2)]X compounds (E = S, Se and Te; X = BF 4 or PF 6). Spectroscopic data and ligand displacement reactions are presented and discussed together with related observations on [C 5H 5Fe(CO) 2(E(CH 3) 2)]BF 4 compounds. The molecular structure of [C 5H 5Fe(P(OCH 3) 3) 2(S(CH 3) 2)]PF 6 was determined by a single-crystal X-ray diffraction study: monoclinic, space group P2 1/ n- C52h (No. 14) with a = 8.4064(12), b = 11.183(2), c = 50.726(8) Å, β = 90.672(13)° and Z = 8 molecules per unit cell. The coordination sphere of the iron atom is pseudo-tetrahedral with an Fe---S bond distance of 2.238 Å. 相似文献
18.
Three families of heterobimetallic compounds were obtained by reaction of [Mo(CO) 3(CH 3CN) 2(Cl)(SnRCl 2)] (R = Ph, Me) with P(4-XC 6H 4) 3 (X = Cl, F, H, Me, MeO). The type of compound obtained dependent on the solvent and concentration of the starting compound. So, [Mo(CO) 2(CH 3COCH 3) 2(PPh 3)(Cl)(SnRCl 2)]· nCH 3COCH 3 (R = Ph, n = 0.5; R = Me, n = 1) (type I) and [Mo(CO) 3{P(4-XC 6H 4) 3}(μ-Cl)(SnRCl 2)] 2 (R = Ph, X = Cl, F, H, Me, MeO; R = Me, X = Cl, F) (type II) were isolated from acetone solution in ca 0.05 M and 0.1 M concentrations, respectively. However, [Mo(CO) 3(CH 3CN) {P(4-XC 6H 4) 3}(Cl)(SnRCl 2)] (R = Ph, X = H; R = Me, X = Cl, F, H) (type III) were obtained from dichloromethane solution independently of the concentration used. All new complexes showed a seven-coordinate environment at molybdenum, containing Mo---Cl and Mo---Sn bonds. Mössbauer spectra indicated a four-coordination at tin for type III complexes. 相似文献
19.
The complex [MoW(μ-CC 6H 4Me-4)(CO) 2(η 7-C 7H 7)(η 5-C 2B 9H 10Me)] reacts with diazomethane in Et 2O containing EtOH to afford the dimetal compound [MoW(OEt)(μ-CH 2){μ-C(C 6H 4Me-4)C(Me)O}(η 7-C 7H 7)(η 5-C 2B 9H 10Me)]. The structure of this product was established by X-ray diffraction. The Mo---W bond [2.778(4) Å] is bridged by a CH 2 group [μ-C---Mo 2.14(3), μ-C---W 2.02(3) Å] and by a C(C 6H 4Me-4)C(Me)O fragment [Mo---O 2.11(3), W---O 2.18(2), Mo---C(C 6H 4Me-4) 2.41(3), W---C(C 6H 4Me-4) 2.09(3), Mo---C(Me) 2.26(3) Å]. The molybdenum atom is η 7-coordinated by the C 7H 7 ring and the tungsten atom is η 5-coordinated by the open pentagonal face of the nido-icosahedral C 2B 9H 10Me cage. The tungsten atom also carries a terminally bound OEt group [W---O 1.88(3) Å]. The 1H and 13C-{ 1H} NMR data for the dimetal compound are reported and discussed. 相似文献
20.
Hydrated rhodium(III) chloride reacts with azobenzene (HAzb) affording RhCl 3(PhNH 2) 2 and the dimeric [(Azb) 2RhCl] 2. The latter reacts with donor ligands to give (Azb) 2RhCl(L), (L=PPh 3, tetrahydrofuran). With [Rh(CO) 2Cl] 2, azobenzene affords an unusual Rh I---Rh III complex, [(Azb) 2RhCl 2Rh(CO) 2], which can also be obtained from [Rh(CO) 2Cl] 2 and [(Azb) 2RhCl] 2. These complexes contain the ortho-metallated (phenylazo)phenyl-2 C,N′ ligand, and their spectroscopic properties are summarised. 相似文献
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