Amidoximes provide facile platinum(II)-mediated oxime-nitrile coupling

The nucleophilic addition of amidoximes R'C(NH(2))═NOH [R' = Me (2.Me), Ph (2.Ph)] to coordinated nitriles in the platinum(II) complexes trans-[PtCl(2)(RCN)(2)] [R = Et (1t.Et), Ph (1t.Ph), NMe(2) (1t.NMe(2))] and cis-[PtCl(2)(RCN)(2)] [R = Et (1c.Et), Ph (1c.Ph), NMe(2) (1c.NMe(2))] proceeds in a 1:1 molar ratio and leads to the monoaddition products trans-[PtCl(RCN){HN═C(R)ONC(R')NH(2)}]Cl [R = NMe(2); R' = Me ([3a]Cl), Ph ([3b]Cl)], cis-[PtCl(2){HN═C(R)ONC(R')NH(2)}] [R = NMe(2); R' = Me (4a), Ph (4b)], and trans/cis-[PtCl(2)(RCN){HN═C(R)ONC(R')NH(2)}] [R = Et; R' = Me (5a, 6a), Ph (5b, 6b); R = Ph; R' = Me (5c, 6c), Ph (5d, 6d), correspondingly]. If the nucleophilic addition proceeds in a 2:1 molar ratio, the reaction gives the bisaddition species trans/cis-[Pt{HN═C(R)ONC(R')NH(2)}(2)]Cl(2) [R = NMe(2); R' = Me ([7a]Cl(2), [8a]Cl(2)), Ph ([7b]Cl(2), [8b]Cl(2))] and trans/cis-[PtCl(2){HN═C(R)ONC(R')NH(2)}(2)] [R = Et; R' = Me (10a), Ph (9b, 10b); R = Ph; R' = Me (9c, 10c), Ph (9d, 10d), respectively]. The reaction of 1 equiv of the corresponding amidoxime and each of [3a]Cl, [3b]Cl, 5b-5d, and 6a-6d leads to [7a]Cl(2), [7b]Cl(2), 9b-9d, and 10a-10d. Open-chain bisaddition species 9b-9d and 10a-10d were transformed to corresponding chelated bisaddition complexes [7d](2+)-[7f](2+) and [8c](2+)-[8f](2+) by the addition of 2 equiv AgNO(3). All of the complexes synthesized bear nitrogen-bound O-iminoacylated amidoxime groups. The obtained complexes were characterized by elemental analyses, high-resolution ESI-MS, IR, and (1)H NMR techniques, while 4a, 4b, 5b, 6d, [7b](Cl)(2), [7d](SO(3)CF(3))(2), [8b](Cl)(2), [8f](NO(3))(2), 9b, and 10b were also characterized by single-crystal X-ray diffraction.     

Preparation of five- and six-coordinate aryl(hydrido) iridium(III) complexes from benzene and functionalized arenes by C-H activation

The reaction of the in situ generated cyclooctene iridium(I) derivative trans-[IrCl(C8H14)(PiPr3)2] with benzene at 80 degrees C gave a mixture of the five-coordinate dihydrido and hydrido(phenyl) iridium(III) complexes [IrH2(Cl)(PiPr3)2] 2 and [IrH(C6H5)(Cl)(PiPr3)2] 3 in the ratio of about 1 : 2. The chloro- and fluoro-substituted arenes C6H5X (X = Cl, F), C6H4F2 and C6H4F(CH3) reacted also by C-H activation to afford the corresponding aryl(hydrido) iridium(III) derivatives [IrH(C6H4X)(Cl)(PiPr3)2] 7, 8, [IrH(C6H3F2)(Cl)(PiPr3)2] 9-11 and [IrH[C6H3F(CH3)](Cl)(PiPr3)2] 12, 13, respectively. The formation of isomeric mixtures had been detected by 1H, 13C, 19F and 31P NMR spectroscopy. Treatment of 3 and 7-13 with CO gave the octahedral carbonyl iridium(III) complexes [IrH(C6H3XX')(Cl)(CO)(PiPr3)2] 5, 14-20 without the elimination of the arene. The reactions of trans-[IrCl(C8H14)(PiPr3)2] with aryl ketones C6H5C(O)R (R = Me, Ph), aryl ketoximes C6H5C(NOH)R (R = Me, Ph) and benzaloxime C6H5C(NOH)H resulted in the formation of six-coordinate aryl(hydrido) iridium(III) compounds 21-25 with the aryl ligand coordinated in a bidentate kappa2-C,O or kappa2-C,N fashion. With C6H5C(O)NH2 as the substrate, the two isomers [IrH[kappa2-N,O-NHC(O)C6H5](Cl)(PiPr3)2] 26 and [IrH[kappa2-C,O-C6H4C(O)NH2](Cl)(PiPr3)2] 27 were prepared stepwise. Treatment of trans-[IrCl(C8H14)(PiPr3)2] with benzoic acid gave the benzoato(hydrido) complex [IrH[kappa2-O,O-O2CC6H5](Cl)(PiPr3)2] 29 which did not rearrange to the kappa2-C,O isomer.     

New and versatile routes to zirconium imido dichloride compounds

Reactions of zirconium dialkyl- or bis(amido)-dichloride complexes "[Zr(CH2SiMe3)2Cl2(Et2O)2]" or [Zr(NMe2)2Cl2(THF)2] with primary alkyl and aryl amines are described. Reaction of "[Zr(CH2SiMe3)2Cl2(Et2O)2]" with RNH2 in THF afforded dimeric [Zr2(mu-NR)2Cl4(THF)4](R=2,6-C6H3iPr2 (1), 2,6-C6H3Me2 (2) or Ph (3)), [Zr2(mu-NR)2Cl4(THF)3](R=tBu (5), iPr (6), CH2Ph (7)), or the "ate" complex [Zr2(mu-NC6F5)2Cl6(THF)2{Li(THF)3}2](4, the LiCl coming from the in situ prepared "[Zr(CH2SiMe3)2Cl2(Et2O)2]"). With [Zr(NMe2)2Cl2(THF)2] the compounds [Zr2(mu-NR)2Cl4(L)x(L')y](R=2,6-C6H3iPr2 (8), 2,6-C6H3Me2 (9), Ph (10) or C6F5 (11); (L)x(L')y=(NHMe2)3(THF), (NHMe2)2(THF)2 or undefined), [Zr2(mu-NtBu)2Cl4(NHMe2)3] (12) and insoluble [Zr(NR)Cl2(NHMe2)]x(R=iPr (13) or CH2Ph (14)) were obtained. Attempts to form monomeric terminal imido compounds by reaction of or with an excess of pyridine led, respectively, to the corresponding dimeric adducts [Zr2(mu-2,6-C6H3Me2)2Cl4(py)4] (15) and [Zr2(mu-NtBu)2Cl4(py)3] (16). The X-ray structures of 1, 2, 4, 8, 12 and 15 have been determined.     

Nitrile-amidine coupling at Pt(IV) and Pt(II) centers. An easy entry to imidoylamidine complexes

Treatment of trans-[PtCl4(RCN)2] (R = Me, Et, Ph, NEt2) with 2 equiv of the amidine PhC(=NH)NHPh in a suspension of MeCN (R = Me), CHCl3 (R = Et, Ph), or in CHCl3 solution (R = NEt2) results in the formation of the imidoylamidine complexes trans-[PtCl4{NH=C(R)N=C(Ph)NHPh}2] (1-4) isolated in good yields (66-84%). The reaction of soluble complexes 3 and 4 with 2 equiv of Ph3P=CHCO2Me in CH2Cl2 (40 degrees C, 5 h) leads to dehydrochlorination resulting in a chelate ring closure to furnish the platinum(IV) chelates [PtCl2{NH=C(R)NC(Ph)=NPh}2] (R = Ph, 5; R = NEt2, 6), accordingly, and the phosphonium salt [Ph3PCH2CO2Me]Cl. Treatment of 5 with 3 equiv of Ph3P=CHCO2Me at 50 degrees C for 5 d resulted in only a 30% conversion to the corresponding Pt(II) complex [Pt{NH=C(NEt2)NC(Ph)=NPh}2] (15). The reduction can be achieved within several minutes, when Ph2PCH2CH2PPh2 in CDCl3 is used. When the platinum(II) complex trans-[PtCl2(RCN)2] is reacted with 2 equiv of the amidine, the imidoylamidinato complexes [PtCl(RCN){NH=C(R)NC(Ph)=NHPh}] (8-11) and [PhC(=NH)NHPh] x HCl (7) are formed. The reaction of trans-[PtCl2(RCN)2] with 4 equiv of the amidine under a prolonged reaction time or treatment of [PtCl(RCN){NH=C(R)NC(Ph)=NHPh}] (8-11) with 2 more equiv of the amidine yields the complex bearing two chelate rings [Pt{NH=C(R)NC(Ph)=NHPh}2] (12-15). The treatment of cis-[PtCl2(RCN)2] (R = Me, Et) with the amidine gives ca. 50-60% yield of [PtCl2{NH=C(R)NHC(Ph)=NHPh}] (16 and 17). All of the platinum compounds were characterized by elemental analyses; FAB mass spectrometry; IR spectroscopy; 1H, 13C{1H}, and 195Pt NMR spectroscopies, and four of them (4, 6, 8, and 15) were also characterized by X-ray crystallography. The coupling of the Pt-bound nitriles and the amidine is metal-mediated insofar as RCN and PhC(=NH)NHPh do not react in the absence of the metal centers in conditions more drastic than those of the observed reactions. The nitrile-amidine coupling reported in this work constitutes a route to the synthesis of imidoylamidine complexes, some of them exhibiting luminescent properties.     

C-Cl bond activation of ortho-chlorinated benzamides by nickel and cobalt compounds supported with phosphine ligands

The C-Cl bonds of ortho-chlorinated benzamides Cl-ortho-C(6)H(4)C(=O)NHR (R = Me (1), nBu (2), Ph (3), (4-Me)Ph (4) and (4-Cl)Ph (5)) were successfully activated by tetrakis(trimethylphosphine)nickel(0) and tetrakis(trimethylphosphine)cobalt(0). The four-coordinate nickel(II) chloride complexes trans-[(C(6)H(4)C([double bond, length as m-dash]O)NHR)Ni(PMe(3))(2)Cl] (R = Me (6), nBu (7), Ph (8) and (4-Me)Ph (9)) as C-Cl bond activation products were obtained without coordination of the amide groups. In the case of 2, the ionic penta-coordinate cobalt(II) chloride [(C(6)H(4)C(=O)NHnBu)Co(PMe(3))(3)]Cl (10) with the [C(phenyl), O(amide)]-chelate coordination as the C-Cl bond activation product was isolated. Under similar reaction conditions, for the benzamides 3-5, hexa-coordinate bis-chelate cobalt(III) complexes (C(6)H(4)C(=O)NHR)Co(Cl-ortho-C(6)H(4)C(=O)NR)(PMe(3))(2) (11-13) were obtained via the reaction with [Co(PMe(3))(4)]. Complexes 11-13 have both a five-membered [C,N]-coordinate chelate ring and a four-membered [N,O]-coordinate chelate ring with two trimethyphosphine ligands in the axial positions. Phosphonium salts [Me(3)P(+)-ortho-C(6)H(4)C(=O)NHR]Cl(-) (R = Ph (14) and (4-Me)Ph (15)) were isolated by reaction of complexes 8 and 9 as a starting material under 1 bar of CO at room temperature. The crystal and molecular structures of complexes 6, 7 and 9-12 were determined by single-crystal X-ray diffraction.     

Halide addition/abstraction in phosphido derivatives: isolation of the thallium and silver intermediates

Reaction of unsaturated (44e (-) skeleton) [PdPt 2(mu-PPh 2) 2(mu-P 2Ph 4)(R F) 4] 4 with Br (-) produces the saturated (48e (-) skeleton) complex [NBu 4][(R F) 2Pt(mu-PPh 2)(mu-Br)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 5 without any M-M' bond. Attempts to eliminate Br (-) of 5 with Ag (+) in CH 2Cl 2 as a solvent gives a mixture of [(R F) 2Pt (III)(mu-PPh 2) 2Pt (III)(R F) 2] and some other unidentified products as a consequence of oxidation and partial fragmentation. However, when the reaction of 5 with Ag (+) is carried out in CH 3CN, no oxidation is observed but the elimination of Br (-) and the formation of [(R F) 2(CH 3CN)Pt(mu-PPh 2)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 6 (46e (-) skeleton), a complex with a Pt-Pd bond, takes place. It is noteworthy that the reaction of 5 with TlPF 6 in CH 2Cl 2 does not precipitate TlBr but forms the adduct [(R F) 2PtTl(mu-PPh 2)(mu-Br)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 7 with a Pt-Tl bond. Likewise, 5 reacts with [AgOClO 3(PPh 3)] in CH 2Cl 2 forming the adduct [AgPdPt 2(mu-Br)(mu-PPh 2) 2(mu-Ph 2P-PPh 2)(R F) 4(PPh 3)] 8, which contains a Pt-Ag bond. Both adducts are unstable in a CH 3CN solution, precipitating TlBr or AgBr and yielding the unsaturated 6. The treatment of [NBu 4] 2[(R F) 2Pt(mu-PPh 2) 2Pd(mu-PPh 2) 2Pt(R F) 2] in CH 3CN with I 2 (1:1 molar ratio) at 233 K yields a mixture of 4 and 6, which after recrystallization from CH 2Cl 2 is totally converted in 4. If the reaction with I 2 is carried out at room temperature, a mixture of the isomers [NBu 4][(R F) 2Pt(mu-PPh 2)(mu-I)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 9 and [NBu 4][(R F)(PPh 2R F)Pt(mu-PPh 2)(mu-I)Pd(mu-PPh 2) 2Pt(R F) 2] 10 are obtained. The structures of the complexes have been established on the bases of NMR data, and the X-ray structures of 5- 8 have been studied. The relationship between the different complexes has been studied.     

Synthesis of monohalogeno derivatives of closo-[B9H9]2-. Crystal structures of (Ph4P)2[1-XB9H8].CH3CN (X = Cl, Br, I)

By reaction of Na2[B9H9] with the appropriate N-halogenosuccinimide, the monohalogenated anion [1-XB9H8]2- (X = Cl, Br, or I) is formed. The X-ray diffraction analyses performed on single crystals of (Ph4P)2[1-XB9H8].CH3CN (X = Cl, Br, I) reveal that the tricapped trigonal prismatic geometry of the cluster is retained after substitution in the 1-position. Crystallographic data are as follows for (Ph4P)2[1-XB9H8].CH3CN. X = Cl, Br: monoclinic, space group P2(1), a = 10.7 A, b = 32.9 A, c = 13.8 A, beta = 96 degrees, Z = 4, R1 = 0.038 and R1 = 0.036, respectively. X = I: monoclinic, space group P2(1)/n, a = 10.5 A, b = 13.6 A, c = 33.4 A, beta = 94 degrees, Z = 4, R1 = 0.094. The compounds have been characterized by vibrational and 11B NMR spectroscopy as well.     

Four‐Membered Heterometallacyclic d0 and d1 Complexes of Group 4 Metallocenes with Amidato Ligands

A study of the coordination chemistry of different amidato ligands [(R)N?C(Ph)O] (R=Ph, 2,6‐diisopropylphenyl (Dipp)) at Group 4 metallocenes is presented. The heterometallacyclic complexes [Cp₂M(Cl){κ²‐N,O‐(R)N?C(Ph)O}] M=Zr, R=Dipp ( 1 a ), Ph ( 1 b ); M=Hf, R=Ph ( 2 )) were synthesized by reaction of [Cp₂MCl₂] with the corresponding deprotonated amides. Complex 1 a was also prepared by direct deprotonation of the amide with Schwartz reagent [Cp₂Zr(H)Cl]. Salt metathesis reaction of [Cp₂Zr(H)Cl] with deprotonated amide [(Dipp)N?C(Ph)O] gave the zirconocene hydrido complex [Cp₂M(H){κ²‐N,O‐(Dipp)N?C(Ph)O}] ( 3 ). Reaction of 1 a with Mg did not result in the desired Zr(III) complex but in formation of Mg complex [(py)₃Mg(Cl) {κ²‐N,O‐(Dipp)N?C(Ph)O}] ( 4 ; py=pyridine). The paramagnetic complexes [Cp′₂Ti{κ²‐N,O‐(R)N?C(Ph)O}] (Cp′=Cp, R=Ph ( 7 a ); Cp′=Cp, R=Dipp ( 7 b ); Cp′=Cp*, R=Ph ( 8 )) were prepared by the reaction of the known titanocene alkyne complexes [Cp₂′Ti(η²‐Me₃SiC₂SiMe₃)] (Cp′=Cp ( 5 ), Cp′=Cp* ( 6 )) with the corresponding amides. Complexes 1 a , 2 , 3 , 4 , 7 a , 7 b , and 8 were characterized by X‐ray crystallography. The structure and bonding of complexes 7 a and 8 were also characterized by EPR spectroscopy.     

铁铂硫原子簇化合物的合成与结构研究 V: [MoFe3S4]类立方烷簇合物的转化反应和[Et4N]3[Mo2Fe6S8(SC6H4CH3-m)3Cl6]的晶体结构

具[MoFe2S4]类立方烷结构单元的双类立方烷化合物[Et4N]4[Mo2Fe7S8(SR)12](1a,R=Ph; 1b, R=tolyl-m)或单类立方烷化合物[MoFe3S4(dteR2)5](2a, R=Me; 2b, R=Et)与酰氯在乙腈中反应, 分别得到不含Fe桥的双类立方烷化合物(Et4N)3[Mo2Fe6S8(SR)3Cl6](3a, R=Ph; 3b, R=toly-m)与[MoFe3S4]骨架支解后的Fe(dteR2)2Cl(4a, R=Me; 4b, R=Et)。说明在相同反应条件下, [MoFe3S4]单元在1中比在2中稳定, 本文首次将1型与3型结构通过一步化学反应连系起来。3型化合物的产生得到X射线衍射测定及^1H NMR谱的证实。本文报道3b的单晶结构及3的^!H NMR数据, 3b属六方晶系, P63/m, a=1.6827(3), c=1.5951(16)nm; V=3.91158nm^3; Dc=1.491g/cm^3;Z=2; F(000)=1780; 偏离因子R=0.048, 化合物2与酰氯反应产生4, 由红外及紫外可见光谱证实。     

MoO2Cl2] as catalyst for hydrosilylation of aldehydes and ketones

The high valent molybdenum-dioxo complex [MoO2Cl2] catalyzes the addition of dimethylphenylsilane to aldehydes and ketones to afford the corresponding dimethylphenylsilyl ethers in quantitative yield.     

The bridging function of an apparently nonbridging ligand: dinuclear rhodium complexes with Rh(mu-SbR3)Rh as a molecular unit

Novel dinuclear rhodium complexes of the general composition [Rh2Cl2(mu-CRR')2(mu-SbiPr3)] (4-6) were prepared by thermolysis of the mononuclear precursors trans-[RhCl(=CRR')(SbiPr3)2] in excellent yield. The X-ray crystal structure analysis of 4 (R = R' = Ph) confirms the symmetrical bridging position of the stibane ligand. Related compounds [Rh2Cl2(mu-CPh2)(mu-CRR')(mu-SbiPr3)] (7, 8) with two different carbene units were obtained either from trans-[RhCl(=CPh2)(SbiPr3)2] (1) and RR'CN2 or by a conproportionation of 4 and 5 (R = R' = p-Tol) or 4 and 6 (R= Ph, R' = p-Tol), respectively. While CO reacts with 4 to give the polymeric product [[RhCl(CPh2)(CO)]n] (9), tert-butyl isocyanide replaces the bridging stibane and yields [Rh2Cl2(mu-CPh2)2(mu-CNtBu)] (10). The reaction of 4 with tertiary phosphanes PR3 leads to complete bridge cleavage and affords the mononuclear compounds trans-[RhCl(=CPh2)(PR3)2] (11-15). In contrast, treatment of 4 with SbMe3 and SbEt3 yields the related triply bridged complexes [Rh2Cl2(mu-CPh2)2(mu-SbR3)] (16, 17) by substitution of SbiPr3 for the smaller stibanes. The displacement of the chloro ligands in 4-6 and 10 by n5-cyclopentadienyl gives the dinuclear complexes [(n5-C5H5)2Rh2(mu-CRR')2] (18-20) and [(n5-C5H5)2Rh2(mu-CPh2)2(mu-CNtBu)] (21), of which 18 (R = R' = Ph) was characterized crystallographically.     

Copper(I) coordination chemistry of (pyridylmethyl)amide ligands

Copper(I) chloro complexes were synthesized with a family of ligands, HL(R) [HL(R) = N-(2-pyridylmethyl)acetamide, R = null; 2-phenyl-N-(2-pyridylmethyl)acetamide, R = Ph; 2,2-dimethyl-N-(2-pyridylmethyl)propionamide, R = Me3; 2,2,2-triphenyl-N-(2-pyridylmethyl)acetamide, R = Ph3)]. Five complexes were synthesized from the respective ligand and cuprous chloride: [Cu(HL)Cl]n (1), [Cu2(HL)4Cl2] (2), [Cu2(HL(Ph))2(CH3CN)2Cl2] (3), [Cu2(HL(Ph)3)2Cl2] (4), and [Cu(HL(Me)3)2Cl] (5). X-ray crystal structures reveal that for all complexes the ligands coordinate to the Cu in a monodentate fashion, and inter- or intramolecular hydrogen-bonding interactions formed between the amide NH group and either amide C=O or chloro groups stabilize these complexes in the solid state and strongly influence the structures formed. Complexes 1-5 display a range of structural motifs, depending on the size of the ligand substituent groups, hydrogen bonding, and the stoichiometry of the starting materials, including a one-dimensional coordination polymer chain (1) and binuclear (2-4) or mononuclear (5) structures.     

Probing the catalytic potential of chloro nitrosyl rhenium(I) complexes

The reduction of the mononitrosyl Re(II) salt [NMe(4)](2)[ReCl(5)(NO)] (1) with zinc in acetonitrile afforded the Re(i) dichloride complex [ReCl(2)(NO)(CH(3)CN)(3)] (2). Subsequent ligand substitution reactions with PCy(3), PiPr(3) and P(p-tolyl)(3) afforded the bisphosphine Re(i) complexes [ReCl(2)(NO)(PR(3))(2)(CH(3)CN)] (3, R = Cy a, iPr b, p-tolyl c) in good yields. The acetonitrile ligand in 3 is labile, permitting its replacement with H(2) (1 bar) to afford the dihydrogen Re(I) complexes [ReCl(2)(NO)(PR(3))(2)(η(2)-H(2))] (4, R = Cy a, iPr b). The catalytic activity of 2, 3 and 4 in hydrogen-related catalyses including dehydrocoupling of Me(2)NH·BH(3), dehydrogenative silylation of styrenes, and hydrosilylation of ketones and aryl aldehydes were investigated, with the main focus on phosphine and halide effects. In the dehydrocoupling of Me(2)NH·BH(3), the phosphine-free complex 2 exhibits the same activity as the bisphosphine-substituted systems. In the dehydrogenative silylation of styrenes, 3a and 4a bearing PCy(3) ligands exhibit high catalytic activities. Monochloro Re(I) hydrides [Re(Cl)(H)(NO)(PR(3))(2)(CH(3)CN)] (5, R = Cy a, iPr b) were proven to be formed in the initiation pathway. The phosphine-free complex 2 showed in dehydrogenative silylations even higher activity than the bisphosphine derivatives, which further emphasizes the importance of a facile phosphine dissociation in the catalytic process. In the hydrosilylation of ketones and aryl aldehydes, at least one rhenium-bound phosphine is required to ensure high catalytic activity.     

Synthesis and structures of selected benzamidinates of Li, Na, Al, Zr and Sn(II) using the C1-symmetric ligands [N(SiMe3)C(C6H4Me-4 or Ph)NPh]-

Several compounds based on the C(1)-symmetric ligands [N(R)C(Ar)NPh]- [abbreviated as B1 (Ar = C(6)H(4)Me-4) or B2 (Ar = Ph), R = SiMe(3)] are reported. They are the crystalline metal benzamidinates [Li(mu:kappa2-B1)(OEt2)](2) (1), [Al(kappa2-B1)2Me] (2), [Al(kappa2-B1)2X] [X = Cl/Me, 1 : 1 (3)], [Sn(kappa2-B1)2] (4), Zr(kappa2-B1)2Cl2 (5), [Zr(kappa2-B1)3Cl] (6), [Na(mu:kappa2-B1)(tmeda)]2 (7), K[B1] (8), Li(B2)(OEt2) (9) and Zr(kappa2-B1)3Cl (10) and the known benzamidine Z-H2NC(C6H4Me-4) = NPh (11). They were prepared by (i) insertion of the nitrile 4-MeC6H4CN (1, 7, 8, 11) or PhCN (9) into the appropriate M-N(R')Ph [R' = R and M = Li (1, 9), Na (7), K (8)] bond and subsequent hydrolysis for 11 [R' = H and M = Li], or (ii) a ligand transfer reaction using the lithium amidinate 1 and Al(Me)2Cl (2, 3), SnCl2 (4) or ZrCl4 (5, 6), or Li(B2) and ZrCl4 (10). The X-ray structures of 1, 2, 3, 4, 6b (i.e..3PhMe) 7, and 11 are presented. Exploratory polymerisation experiments are described, using 2, 5 or 6 as a procatalyst with methylaluminoxane (MAO) (Al : Zr ca. 500 : 1) as promoter. Thus toluene solutions were exposed to C2H4 under ambient conditions; while 2 was unresponsive, 5 and 6 showed modest activity in the formation of polyethylene.     

Synthesis and Crystal Structure of [H-amp]4[Mo8O26（DMF）2].2H2O（amp = 2-Amino-6-methyl-pyridine）

1INTRODUCTIONMetal-oxoclusterchemistryhasbeenactivelypurchasedduetotheinterestinchemistryitselfanditsvariousapplicationsinfieldssuchascatalysis,electronicconductivity,magnetism,nonlinearopti-calpropertiesandmedicine[1～3].Recently,anim-portantadvanceinmet…     

Synthesis and reactivity of Ir(I) and Ir(III) complexes with MeNH2, Me2C=NR (R = H, Me), C,N-C6H4{C(Me)=N(Me)}-2, and N,N'-RN=C(Me)CH2C(Me2)NHR (R = H, Me) ligands

Complexes [Ir(Cp*)Cl(n)(NH2Me)(3-n)]X(m) (n = 2, m = 0 (1), n = 1, m = 1, X = Cl (2a), n = 0, m = 2, X = OTf (3)) are obtained by reacting [Ir(Cp*)Cl(mu-Cl)]2 with MeNH2 (1:2 or 1:8) or with [Ag(NH2Me)2]OTf (1:4), respectively. Complex 2b (n = 1, m = 1, X = ClO 4) is obtained from 2a and NaClO4 x H2O. The reaction of 3 with MeC(O)Ph at 80 degrees C gives [Ir(Cp*){C,N-C6H4{C(Me)=N(Me)}-2}(NH2Me)]OTf (4), which in turn reacts with RNC to give [Ir(Cp*){C,N-C6H4{C(Me)=N(Me)}-2}(CNR)]OTf (R = (t)Bu (5), Xy (6)). [Ir(mu-Cl)(COD)]2 reacts with [Ag{N(R)=CMe2}2]X (1:2) to give [Ir{N(R)=CMe2}2(COD)]X (R = H, X = ClO4 (7); R = Me, X = OTf (8)). Complexes [Ir(CO)2(NH=CMe2)2]ClO4 (9) and [IrCl{N(R)=CMe2}(COD)] (R = H (10), Me (11)) are obtained from the appropriate [Ir{N(R)=CMe2}2(COD)]X and CO or Me4NCl, respectively. [Ir(Cp*)Cl(mu-Cl)]2 reacts with [Au(NH=CMe2)(PPh3)]ClO4 (1:2) to give [Ir(Cp*)(mu-Cl)(NH=CMe2)]2(ClO4)2 (12) which in turn reacts with PPh 3 or Me4NCl (1:2) to give [Ir(Cp*)Cl(NH=CMe2)(PPh3)]ClO4 (13) or [Ir(Cp*)Cl2(NH=CMe2)] (14), respectively. Complex 14 hydrolyzes in a CH2Cl2/Et2O solution to give [Ir(Cp*)Cl2(NH3)] (15). The reaction of [Ir(Cp*)Cl(mu-Cl)]2 with [Ag(NH=CMe2)2]ClO4 (1:4) gives [Ir(Cp*)(NH=CMe2)3](ClO4)2 (16a), which reacts with PPNCl (PPN = Ph3=P=N=PPh3) under different reaction conditions to give [Ir(Cp*)(NH=CMe2)3]XY (X = Cl, Y = ClO4 (16b); X = Y = Cl (16c)). Equimolar amounts of 14 and 16a react to give [Ir(Cp*)Cl(NH=CMe2)2]ClO4 (17), which in turn reacts with PPNCl to give [Ir(Cp*)Cl(H-imam)]Cl (R-imam = N,N'-N(R)=C(Me)CH2C(Me)2NHR (18a)]. Complexes [Ir(Cp*)Cl(R-imam)]ClO4 (R = H (18b), Me (19)) are obtained from 18a and AgClO4 or by refluxing 2b in acetone for 7 h, respectively. They react with AgClO4 and the appropriate neutral ligand or with [Ag(NH=CMe2)2]ClO4 to give [Ir(Cp*)(R-imam)L](ClO4)2 (R = H, L = (t)BuNC (20), XyNC (21); R = Me, L = MeCN (22)) or [Ir(Cp*)(H-imam)(NH=CMe2)](ClO4)2 (23a), respectively. The later reacts with PPNCl to give [Ir(Cp*)(H-imam)(NH=CMe2)]Cl(ClO4) (23b). The reaction of 22 with XyNC gives [Ir(Cp*)(Me-imam)(CNXy)](ClO4)2 (24). The structures of complexes 15, 16c and 18b have been solved by X-ray diffraction methods.     

Cobalt-catalyzed regioselective carbocyclization reaction of o-iodophenyl ketones and aldehydes with alkynes, acrylates, and acrylonitrile: a facile route to indenols and indenes

An efficient cobalt-catalyzed carbocylization for the synthesis of indenols and indenes and a new method for reductive decyanation are described. 2-Iodophenyl ketones and aldehydes 1a-g undergo carbocyclization with various disubstituted alkynes 2a-k in the presence of Co(dppe)I(2) and zinc powder in acetonitrile at 80 degrees C for 3 h to afford the corresponding indenol derivatives 3a-s and4a-m in good to excellent yields. For some unsymmetrical alkynes, the carbocyclization was remarkably regioselective, affording a single regioisomer. The cobalt-catalyzed carbocyclization reaction was successfully extended to the synthesis of indene derivatives. Thus, the reaction of 2-iodophenyl ketones and aldehydes (1) with acrylates H(2)C=CHCO(2)R (7a-d) and acrylonitrile H(2)C=CHCN (7e) proceeds smoothly in the presence of Co(dppe)Cl(2)/dppe and zinc powder in acetonitrile at 80 degrees C for 24 h to afford the corresponding indenes 8a-k and 9a-c in moderate to good yields. Interestingly, when 7e was employed for the carbocylization, reductive decyanation also occurred to give an indene derivative without the cyano functionality. A possible mechanism for this cobalt-catalyzed carbocyclization reaction is also proposed.     

ａ,β不饱和醛的均相催化氢硅化反应

本文对ａ,β-不饱和醛的均相催化氢硅化反应作了定量研究.采用假一级动力学的方法,用气相色谱跟踪监测反应速度,定量研究反应活性与反应物结构的关系,进一步探讨反应的可能机理.     

Primary and secondary phosphine complexes of iron porphyrins and ruthenium phthalocyanine: synthesis, structure, and P-H bond functionalization

Reduction of [Fe(III)(Por)Cl] (Por = porphyrinato dianion) with Na2S2O4 followed by reaction with excess PH2Ph, PH2Ad, or PHPh2 afforded [Fe(II)(F20-TPP)(PH2Ph)2] (1a), [Fe(II)(F20-TPP)(PH2Ad)2] (1b), [Fe(II)(F20-TPP)(PHPh2)2] (2a), and [Fe(II)(2,6-Cl2TPP)(PHPh2)2] (2b). Reaction of [Ru(II)(Pc)(DMSO)2] (Pc = phthalocyaninato dianion) with PH2Ph or PHPh2 gave [Ru(II)(Pc)(PH2Ph)2] (3a) and [Ru(II)(Pc)(PHPh2)2] (4). [Ru(II)(Pc)(PH2Ad)2] (3b) and [Ru(II)(Pc)(PH2Bu(t))2] (3c) were isolated by treating a mixture of [Ru(II)(Pc)(DMSO)2] and O=PCl2Ad or PCl2Bu(t) with LiAlH4. Hydrophosphination of CH2=CHR (R = CO2Et, CN) with [Ru(II)(F20-TPP)(PH2Ph)2] or [Ru(II)(F20-TPP)(PHPh2)2] in the presence of (t)BuOK led to the isolation of [Ru(II)(F20-TPP)(P(CH2CH2R)2Ph)2] (R = CO2Et, 5a; CN, 5b) and [Ru(II)(F20-TPP)(P(CH2CH2R)Ph2)2] (R = CO2Et, 6a; CN, 6b). Similar reaction of 3a with CH2=CHCN or MeI gave [Ru(II)(Pc)(P(CH2CH2CN)2Ph)2] (7) or [Ru(II)(Pc)(PMe2Ph)2] (8). The reactions of 4 with CH2=CHR (R = CO2Et, CN, C(O)Me, P(O)(OEt)2, S(O)2Ph), CH2=C(Me)CO2Me, CH(CO2Me)=CHCO2Me, MeI, BnCl, and RBr (R = (n)Bu, CH2=CHCH2, MeC[triple bond]CCH2, HC[triple bond]CCH2) in the presence of (t)BuOK afforded [Ru(II)(Pc)(P(CH2CH2R)Ph2)2] (R = CO2Et, 9a; CN, 9b; C(O)Me, 9c; P(O)(OEt)2, 9d; S(O)2Ph, 9e), [Ru(II)(Pc)(P(CH2CH(Me)CO2Me)Ph2)2] (9f), [Ru(II)(Pc)(P(CH(CO2Me)CH2CO2Me)Ph2)2] (9g), and [Ru(II)(Pc)(PRPh2)2] (R = Me, 10a; Bu(n), 10b; Bn, 10c; CH2CH=CH2, 10d; CH2C[triple bond]CMe, 10e; CH=C=CH2, 10f). X-ray crystal structure determinations revealed Fe-P distances of 2.2597(9) (1a) and 2.309(2) A (2bx 2 CH2Cl2) and Ru-P distances of 2.3707(13) (3b), 2.373(2) (3c), 2.3478(11) (4), and 2.3754(10) A (5b x 2 CH2Cl2). Both the crystal structures of 3b and 4 feature intermolecular C-H...pi interactions, which link the molecules into 3D and 2D networks, respectively.     

Reactivity of niobium(v) and tantalum(v) halides with carbonyl compounds: synthesis of simple coordination adducts, C-H bond activation, C=O protonation, and halide transfer

The metal halides of Group 5 MX(5) (M = Nb, Ta; X = F, Cl, Br) react with ketones and acetylacetones affording the octahedral complexes [MX(5)(ketone)] () and [TaX(4){kappa(2)(O)-OC(Me)C(R)C(Me)O}] (R = H, Me, ), respectively. The adducts [MX(5)(acetone)] are still reactive towards acetone, acetophenone or benzophenone, giving the aldolate species [MX(4){kappa(2)(O)-OC(Me)CH(2)C(R)(R')O}] (). The syntheses of (M = Ta, X = F, R = R' = Ph) and (M = Ta, X = Cl, R = Me, R' = Ph) take place with concomitant formation of [(Ph(2)CO)(2)-H][TaF(6)], and [(MePhCO)(2)-H][TaCl(6)], respectively. The compounds [acacH(2)][TaF(6)], and [TaF{OC(Me)C(Me)C(Me)O}(3)][TaF(6)], have been isolated as by-products in the reactions of TaF(5) with acacH and 3-methyl-2,4-pentanedione, respectively. The molecular structures of, and have been ascertained by single crystal X-ray diffraction studies.