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1.
The Pd-catalyzed reaction of [CpCo(S2C2(Ph)(Bpin))] (1, Bpin = 4,4,5,5-tetramethyl-1,3,2-dioxaboronate) with 1-iodonaphthalene or 2-bromothiophene gave the cross-coupling product [CpCo(S2C2(Ph)(Ar))] (Ar = 1-Np (4) or 2-Th (5)), although an early paper described the reaction of 1 with 3-bromopyridine or 9-bromoanthracene (Ar = 3-Py (2) or 9-Anth (3)). The boronation of the brominated precursor [CpCo(S2C2(p-C6H4Br)(H))] (7) with Bpin-H in the presence of Pd catalyst gave the expected boronated product [CpCo(S2C2(p-C6H4Bpin)(H))] (8) but also underwent an unexpected direct boronation on the dithiolene carbon to form [CpCo(S2C2(p-C6H4Br)(Bpin))] (9). The brominated complex 7 or [CpCo(S2C2(Ph)(p-C6H4Br))] (10) was synthesized by thermal reaction and the microwave-enhanced reaction relatively gave better yield with shorter reaction time than that of the conventional heating reaction. The cross-coupling reactions of the boronated or [CpCo(S2C2(Ph)(p-C6H4Bpin))] (11) with aryl halides successfully produced the corresponding cross-coupling products such as [CpCo(S2C2(p-C6H4Py)(H))] (12) or [CpCo(S2C2(p-C6H4Anth)(H))] (13) from 8 and [CpCo(S2C2(Ph)(p-C6H4Py))] (14) from 11. The structures of 7, 9, 11, 12, 13 and 14 were determined by X-ray diffraction studies. Electronic absorption maxima (λmax) due to dithiolene LMCT in dichloromethane solution can be modified in the range of 574-602 nm by a substituent effect on the dithiolene ring. Redox potentials obtained from CV measurement were also reported.  相似文献   

2.
Tetracyanoethylene oxide (TCNEO) reacted with [CpCo(dithiolene)] (Cp = η5-cyclopentadienyl) complexes having 4-pyridyl or 3-pyridyl group to undergo a dicyanomethylation to the nitrogen atom on the pyridyl group. The reaction of [CpCo(S2C2(4Py)2)] (1) with TCNEO formed both the monodicyanomethylated [CpCo(S2C2(4Py)(4Py-C(CN)2))] (1a) and bisdicyanomethylated [CpCo(S2C2(4Py-C(CN)2)2)] (1b). [CpCo(S2C2(2Py)(4Py))] (2) reacted with TCNEO to give [CpCo(S2C2(2Py)(4Py-C(CN)2))] (2a) but no dicyanomethylation occurred on the 2-pyridyl group. 2 reacted with excess TCNEO to form the only dicyanomethylated acetylene derivative 2Py-CC-(4Py-C(CN)2) (2c), followed by a dissociation of the CpCoS2 fragment. The monodicyanomethylated [CpCo(S2C2(nPy-C(CN)2)(2-thienyl))] (n = 4 (4a) or 3 (5a)) complexes were also prepared from [CpCo(S2C2(nPy)(2-thienyl))] (n = 4 (4) or 3 (5)) and TCNEO. 1b was structurally characterized by X-ray diffraction study. The all dicyanomethylated [CpCo(dithiolene)] complexes showed the dithiolene LMCT absorption in the range of 605-644 nm (ε = 7000-9200 M−1 cm−1) and very strong absorption due to their pyridinium-dicyanomethylide moieties in near-UV region (e.g. 1b: λmax = 470 nm, ε = 43,400 M−1 cm−1). The CV of the all dicyanomethylated complexes exhibited two reduction waves. The first reduction is due to CoIII/CoII and the second one is due to the reduction of the pyridinium-dicyanomethylide moiety. The reduced 1b is stable enough for several minutes according to the visible spectroelectrochemical measurement. The ESR spectrum of 1b indicated eight hyperfine splittings due only to the interaction with the nuclear spin of cobalt (I = 7/2).  相似文献   

3.
This review paper summarizes the reactivities of metal dithiolene complexes based on the ‘coexistence of aromaticity and unsaturation’ in the five-membered metallacycle, the so-called metalladithiolene ring (MS2C2). The 16-electron [LM(dithiolene)] (LM = CpMIII, Cp*MIII, (C6R6)MII) complexes are coordinatively unsaturated and usually show M-S centered cycloaddition reactions with nucleophiles (e.g. diazoalkanes, organic azides, quadricyclane) and electrophiles (e.g. tetracyanoethylene oxide, activated acetylene). The resulting metalladithiolene cycloadducts, which have three-membered M-S-C or M-S-N rings, further react with protic acids or PR3 to undergo the ring-opening reactions involving the M-C bond, M-S bond or M-N bond cleavages. Furthermore, diverse adduct dissociations are observed by thermal, photochemical or electrochemical redox reactions. Such reactions normally produce the original [LM(dithiolene)] complexes (non-adduct) and the eliminated fragments. Among them, the Co-S centered imido adduct [CpCo(dithiolene)(NR)] (R = Ts, Ms) reacted under thermal conditions in the presence of PR3 to undergo the intramolecular imido migration reaction to the Cp ligand, giving [(C5H4-NHR)Co(dithiolene)] complexes. The M-S centered multinuclear cluster complexes are obtained by the reaction of [LM(dithiolene)] with low valent M(CO)n complexes. The square-planar bis(dithiolene) complexes [M(dithiolene)2]0 (M = Ni, Pd, Pt) or tris(dithiolene) complexes [M(dithiolene)3]0 yield cycloaddition products with olefins. These reactions are due to ligand centered reactions made possible by a molecular orbital overlap between dithiolene LUMO and olefin HOMO. Similar ligand centered adducts are obtained by the reaction of dianionic [M(dithiolene)2]2− with haloalkanes or dihaloalkanes. Also these adducts of bis(dithiolene) complex are dissociated photochemically and electrochemically. This paper also describes the reactivities of organometallic o-carborane dithiolate complexes, which are generally formulated as [LM(S2C2B10H10)] (LM = CpCo, Cp*Rh, Cp*Ir, (p-cymene)Ru and (p-cymene)Os). Diverse addition reactions are reported; in particular, the reaction with acetylene involves B-H bond activation in the carborane moiety.  相似文献   

4.
Eight new sulfur-rich [CpCo(dithiolene)] complexes were synthesized from [Zn(dmit)2]2− as a starting material. The structures, electrochemical behavior and electronic absorption spectra of the sulfur-rich [CpCo(S2C2S2Y)] complexes could be compared with the early data of analogous Ni complexes. [CpCo(pddt)] (Y = -(CH2)3-), [CpCo(dpdt)] (Y = -CH2C(CH2)CH2-), [CpCo(bddt)] (Y = -(CH2)4-), [CpCo(dtdt)] (Y = -CH2SCH2-) and [CpCo(poddt)] (Y = -CH2C(O)CH2-) crystallized in all isostructural with the corresponding paramagnetic [CpNi(dithiolene)] complexes, but [CpCo(dmid)] (Y = CO), [CpCo(dddt)] (Y = -(CH2)2-) and [CpCo(F2pddt)] (Y = -CH2CF2CH2-) crystallized in non-isostructural with them. These molecules are associated with intermolecular short S?S contacts in the crystals. [CpCo(F2pddt)] did not show any remarkable S?S contacts but indicated interesting fluorine segregation and Cp?Cp face-to-face interactions. Redox potentials of [CpCo(dithiolene)] complexes were obtained with the cyclic voltammetry measurements and dimerized by electrochemical oxidations. Electronic absorption spectra of [CpCo(dithiolene)] complexes showed visible absorption in the range of 585-701 nm as lowest energy wavelengths (? = 9800-11,800 M−1 cm−1) in solutions, and they were higher energy than those of [CpNi(dithiolene)] complexes (near-IR).  相似文献   

5.
A family of eight neutral, pseudotetrahedral piano-stool ruthenium complexes C, of the type [RuCl2(p-cymene)(PArPhR)] (Ar = 1-naphthyl, 9-phenanthryl and 2-biphenylyl; R = Me, i-Pr, OMe, –CH2SiMe3 and –CH2SiPh3) have been prepared and characterised, including the X-ray crystal structure for C6 (Ar = 2-biphenylyl; R = i-Pr). These complexes catalyse the asymmetric hydrogen transfer reaction of acetophenone in refluxing 2-propanol in the presence of potassium tert-butoxyde, reaching full conversions and up to 45% ee after 24 h towards the S enantiomer of 1-phenylethanol. Cationic complexes formed upon treatment of C with one equivalent of AgSbF6 or (Et3O)PF6 are active in the cyclopropanation reaction of styrene and α-methylstyrene by ethyl diazoacetate. Low to moderate conversions (up to 58%), diastereoselectivities (up to 40% de), and moderate enantioselectivities (up to 69% ee) have been found. For both reactions, bulky complexes and C6 in particular lead to the best results.  相似文献   

6.
A family of eight neutral, pseudotetrahedral piano-stool ruthenium complexes C, of the type [RuCl2(p-cymene)(PArPhR)] (Ar = 1-naphthyl, 9-phenanthryl and 2-biphenylyl; R = Me, i-Pr, OMe, –CH2SiMe3 and –CH2SiPh3) have been prepared and characterised, including the X-ray crystal structure for C6 (Ar = 2-biphenylyl; R = i-Pr). These complexes catalyse the asymmetric hydrogen transfer reaction of acetophenone in refluxing 2-propanol in the presence of potassium tert-butoxyde, reaching full conversions and up to 45% ee after 24 h towards the S enantiomer of 1-phenylethanol. Cationic complexes formed upon treatment of C with one equivalent of AgSbF6 or (Et3O)PF6 are active in the cyclopropanation reaction of styrene and α-methylstyrene by ethyl diazoacetate. Low to moderate conversions (up to 58%), diastereoselectivities (up to 40% de), and moderate enantioselectivities (up to 69% ee) have been found. For both reactions, bulky complexes and C6 in particular lead to the best results.  相似文献   

7.
[CpCo(oxddt)] complex (2, oxddt = o-xylenediyldithioethylene-1,2-dithiolate, Cp = η5-cyclopentadienyl) was obtained from o-xylenediyldithioethylene-1,3-dithiol-2-one (OC(oxddt)) (1). 2 further reacted with diazoalkanes (N2CHR) to form some alkylidene-bridged adducts [CpCo(CHR)(oxddt)] (R = H (3a), SiMe3 (3b)). Adduct 3a further reacted with protic acids (HX) to give some S-methylated adducts [CpCo(X)(oxddt)(S-Me)] (X = Cl (4a), OCOCF3 (4c)), followed by the Co-C bond cleavage in the three-membered cobaltathiirane ring. Two different Z-shaped and U-shaped molecular structures were observed by X-ray diffraction studies. In the former structure (Z), the dithiolene and o-xylylene planes are located at almost parallel position each other, and in the latter structure (U), both planes are not parallel but the o-xylylene moiety is located closer to the dithiolene plane than the Z-shaped one. The Z-shaped structure involves 1 and 2. The U-shaped structure involves 3a, 3b, 4a and 4c. Complex 1 showed a one-dimensional chain through intermolecular π-π interaction in the crystal. Complex 2 had a dimeric interaction between dithioethylenedithiolate moieties (S2C2S2) in the oxddt. The SiMe3 group in 3b was placed at an exo-position with respect to the cobaltadithiolene ring due to a steric hindrance from the U-shaped oxddt ligand. In 4a, the X and Me groups are located at the opposite side of the dithiolene plane (anti-form) but in 4c, both groups are presented at the same side of the dithiolene plane (syn-form). The NMR analysis of 4a in solution indicated existence of both anti- and syn-isomers (7:1).  相似文献   

8.
The synthesis of a series of ruthenium 1,5-disubstituted 1,2,3-triazolato complexes, 1,5-disubstituted 1,2,3-triazoles, and a triazolium salt is reported. Treatment of the ruthenium azido complex [Ru]-N3 ( 1 , [Ru] = (η5-C5H5)(dppe)Ru, dppe = Ph2PCH2CH2PPh2) with an excess of ethyl propiolate results in the formation of a mixture of the Z- and E-forms of zwitterionic N(1)-bound N(3)-ethyl acryl-4-carboxylate triazolato complexes [Ru]N3(CH=CHCO2Et)C2H(CO2) ( Z - 2 ) and ( E - 2 ). The arylation of 2 with aromatic bromides gives a series of cationic N(1)-bound N(3)-ethyl acryl-4-alkoxycarbonyl triazolato complexes {[Ru]N3(CH=CHCO2Et)C2H(CO2CH2R)}[Br] ( 3a , R = Ph ; 3b , R = C6F5; 3c , R = 4-C6H4CN, 3d , R = 2,6-C6H3F2) and the subsequent cleavage of the Ru-N bond of 3a–d gives 1,5-disubstituted 1,2,3-triazoles N3(CH=CHCO2Et)C2H(CO2CH2R) ( 4a , R = Ph; 4b , R = C6F5; 4c , R = 4-C6H4CN; 4d , R = 2,6-C6H3F2) and [Ru]-Br. A 1,2,3-triazolium salt [N3(CH=CHCO2Et)(CH2C6F5)C2H2][Br] ( 5 ) was formed by transformation of 4b in BrCH2C6F5/chloroform mixture. The structures of Z-3a and Z-5 were confirmed by single-crystal x-ray diffraction analysis and both complexes participate in non-covalent aromatic interactions in the solid-state structures which can be favorable in the binding of DNA/biomolecular targets and have shown great potential in the application of biologically active anticancer drugs.  相似文献   

9.
Azido coordinated dithiolene complexes [CpCo(N3){S2C2(CO2Me)2}(S-CHR1R2)], where R1, R2 = H (4a); R1 = H, R2 = SiMe3 (4b); R1 = H, R2 = CO2Et (4c), were synthesized by the reactions of the corresponding Cl coordinated precursors [CpCo(Cl){S2C2(CO2Me)2}(S-CHR1R2)] (3a-3c) with sodium azide. The Cl coordinated complex 3d (R1, R2 = CO2Me) did not produce any N3 coordinated complexes but formed the CR1R2-bridged alkylidene adduct [CpCo{S2C2(CO2Me)2}(CR1R2)] (2d; R1, R2 = CO2Me). The structure of 4a was determined by X-ray diffraction study. In the molecular structure of 4a, the coordinated N3 ligand and CHR1R2 group were located at the same side with respect to the dithiolene ring (syn form), although the corresponding Cl precursor (3a; R1, R2 = H) was anti form. A structural conversion of syn/anti was conceivable during the Cl/N3 ligand exchange. Thermal (80 °C) and photochemical reactions (Hg lamp) of 4a-4c were performed. Among them, 4c was relatively well reacted compared with the others to form the CR1R2-bridged alkylidene adduct (2c; R1 = H, R2 = CO2Et), followed by a formal HN3 elimination, and the reaction also produced non-adduct of the cobalt dithiolene complex [CpCo{S2C2(CO2Me)2}] (1). The electrochemical 1e reduction of 4c underwent a formal N3 ligand elimination, and successive second reduction caused the CHR1R2 group elimination or reformed the CR1R2-bridged alkylidene adduct 2c.  相似文献   

10.
The reactions of [M2Cl2(μ-Cl)2(PMe2Ph)2] with mercapto-o-carboranes in the presence of pyridine afforded mono-nuclear complexes of composition, [MCl(SCb°R)(py)(PMe2Ph)] (M = Pd or Pt; Cb° = o-C2B10H10; R = H or Ph). The treatment of [PdCl2(PEt3)2] with PhCb°SH yielded trans-[Pd(SCb°Ph)2(PEt3)2] (4) which when left in solution in the presence of pyridine gave another substitution product, [Pd(SCb°Ph)2(py)(PEt3)] (5). The structures of [PdCl(SCb°Ph)(py)(PMe2Ph)] (1), [Pd(SCb°Ph)2(PEt3)2] (4) and [Pd(SCboPh)2(py)(PEt3)] (5) were established unambiguously by X-ray crystallography. The palladium atom in these complexes adopts a distorted square-planar configuration with neutral donor atoms occupying the trans positions. Thermolysis of [PdCl(SCb°)(py)(PMe2Ph)] (2) in TOPO (trioctylphosphine oxide) at 200 °C gave nanocrystals of TOPO capped Pd4S which were characterized by XRD pattern and SEM.  相似文献   

11.
The bridging aminocarbyne complexes [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)2(Cp)2][SO3CF3] (R = Me, 1a; Xyl, 1b; 4-C6H4OMe, 1c; Xyl = 2,6-Me2C6 H3) react with acrylonitrile or methyl acrylate, in the presence of Me3NO and NaH, to give the corresponding μ-allylidene complexes [Fe2{μ-η13- Cα(N(Me)(R))Cβ(H)Cγ(H)(R′)}(μ-CO)(CO)(Cp)2] (R = Me, R′ = CN, 3a; R = Xyl, R′ = CN, 3b; R = 4-C6H4OMe, R′ = CN, 3c; R = Me, R′ = CO2Me, 3d; R = 4-C6H4OMe, R′ = CO2Me, 3e). Likewise, 1a reacts with styrene or diethyl maleate, under the same reaction conditions, affording the complexes [Fe2{μ-η13-Cα(NMe2)Cβ(R′)Cγ(H)(R″)}(μ-CO)(CO)(Cp)2] (R′ = H, R″ = C6H5, 3f; R′ = R″ = CO2Et, 3g). The corresponding reactions of [Ru2{μ-CN(Me)(CH2Ph)}(μ-CO)(CO)2(Cp)2][SO3CF3] (1d) with acrylonitrile or methyl acrylate afford the complexes [Ru2{μ-η13-Cα(N(Me)(CH2Ph))Cβ(H)Cγ(H)(R′)}(μ-CO)(CO)(Cp)2] (R′ = CN, 3h; CO2Me, 3i), respectively.The coupling reaction of olefin with the carbyne carbon is regio- and stereospecific, leading to the formation of only one isomer. C-C bond formation occurs selectively between the less substituted alkene carbon and the aminocarbyne, and the Cβ-H, Cγ-H hydrogen atoms are mutually trans.The reactions with acrylonitrile, leading to 3a-c and 3h involve, as intermediate species, the nitrile complexes [M2{μ-CN(Me)(R)}(μ-CO)(CO)(NC-CHCH2)(Cp)2][SO3CF3] (M = Fe, R = Me, 4a; M = Fe, R = Xyl, 4b; M = Fe, R = 4-C6H4OMe, 4c; M = Ru, R = CH2C6H5, 4d).Compounds 3a, 3d and 3f undergo methylation (by CH3SO3CF3) and protonation (by HSO3CF3) at the nitrogen atom, leading to the formation of the cationic complexes [Fe2{μ-η13-Cα(N(Me)3)Cβ(H)Cγ(H)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R = CN, 5a; R = CO2Me, 5b; R = C6H5, 5c) and [Fe2{μ-η13-Cα(N(H)(Me)2)Cβ(H)Cγ(H)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R = CN, 6a; R = CO2Me, 6b; R = C6H5, 6c), respectively.Complex 3a, adds the fragment [Fe(CO)2(THF)(Cp)]+, through the nitrile functionality of the bridging ligand, leading to the formation of the complex [Fe2{μ-η13-Cα(NMe2)Cβ(H)Cγ(H)(CNFe(CO)2Cp)}(μ-CO)(CO)(Cp)2][SO3CF3] (9).In an analogous reaction, 3a and [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)2(Cp)2][SO3CF3], in the presence of Me3NO, are assembled to give the tetrameric species [Fe2{μ-η13-Cα(NMe2)Cβ(H)Cγ(H)(CN[Fe2{μ- CN(Me)(R)}(μ-CO)(CO)(Cp)2])}(μ-CO)(CO)(Cp)2][SO3CF3] (R = Me, 10a; R = Xyl, 10b; R = 4-C6H4OMe, 10c).The molecular structures of 3a and 3b have been determined by X-ray diffraction studies.  相似文献   

12.
The neutral arene ruthenium azido complexes [(η6-p-cymene)Ru(LL)(N3)], [LL = acetylacetonato (acac) (4), benzoylacetonato (bzac) (5) diphenylbenzoyl methane (dbzm) (6)] undergo [3+2] cycloaddition reaction with a series of activated alkynes and fumaronitrile to produce the arene ruthenium triazolato complexes: [(η6-p-cymene)Ru(LL){N3C2(CO2R)2}] [LL = (acac), R = Me (7); LL = (bzac), R = Me (8); LL = (dbzm), R = Me (9); LL = (acac), R = Et (10); LL = (bzac), R = Et (11); LL = (dbzm), R = Et (12) and [(η6-p-cymene)Ru(LL)(N3C2HCN)]; LL = acac (13), bzac (14); dbzm (15). However, cationic azido complexes, [(η6-p-cymene)Ru(dppe)(N3)]+ and [(η6-p-cymene)Ru(dppm)(N3)]+ do not undergo such cycloaddition reactions. The complexes were characterized on the basis of microanalyses, FT-IR and NMR spectroscopic data. Crystal structures of representative complexes were determined by single crystal X-ray diffraction.  相似文献   

13.
New μ-vinylalkylidene complexes cis-[Fe2{μ-η13-Cγ(R′)Cβ(R″)CαHN(Me)(R)}(μ-CO)(CO)(Cp)2] (R = Me, R′ = R″ = Me, 3a; R = Me, R′ = R″ = Et, 3b; R = Me, R′ = R″ = Ph, 3c; R = CH2Ph, R′ = R″ = Me, 3d; R = CH2Ph, R′ = R″ = COOMe, 3e; R = CH2 Ph, R′ = SiMe3, R″ = Me, 3f) have been obtained b yreacting the corresponding vinyliminium complexes [Fe2{μ-η13-Cγ(R′)Cβ(R″)CαN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (2a-f) with NaBH4. The formation of 3a-f occurs via selective hydride addition at the iminium carbon (Cα) of the precursors 2a-f. By contrast, the vinyliminium cis-[Fe2{μ-η13-Cγ (R′) = Cβ(R″)Cα = N(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3] (R′ = R″ = COOMe, 4a; R′ = R″ = Me, 4b; R′ = Prn, R″ = Me, 4c; Prn = CH2CH2CH3, Xyl = 2,6-Me2C6H3) undergo H addition at the adjacent Cβ, affording the bis-alkylidene complexes cis-[Fe2{μ-η12-C(R′)C(H)(R″)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2], (5a-c). The cis and trans isomers of [Fe2{μ-η13-Cγ(Et)Cβ(Et)CαN(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3] (4d) react differently with NaBH4: the former reacts at Cα yielding cis-[Fe2{μ-η13-Cγ(Et)Cβ(Et)CαHN(Me)(Xyl)}(μ-CO)(CO)(Cp)2], 6a, whereas the hydride attack occurs at Cβ of the latter, leading to the formation of the bis alkylidene trans-[Fe2{μ-η12-C(Et)C(H)(Et)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2] (5d). The structure of 5d has been determined by an X-ray diffraction study. Other μ-vinylalkylidene complexes cis-[Fe2{μ-η13-Cγ(R′)Cβ(R″)CαHN(Me)(Xyl)}(μ-CO)(CO)(Cp)2], (R′ = R″ = Ph, 6b; R′ = R″ = Me, 6c) have been prepared, and the structure of 6c has been determined by X-ray diffraction. Compound 6b results from treatment of cis-[Fe2{μ-η13-Cγ(Ph)Cβ(Ph)CαN(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3] (4e) with NaBH4, whereas 6c has been obtained by reacting 4b with LiHBEt3. Both cis-4d and trans-4d react with LiHBEt3 affording cis-6a.  相似文献   

14.
Tricarbonyl-η5-pentadienylmanganese reacts with mercaptans RSH, R = Ph, C6F5, m-NH2C6H4, p-NH2C6H4, and HSCH2CH2 in the presence of ECH2CH2E, E = -PPh2 or -NH2 to give novel stable terminal thiolate mononuclear complexes fac-Mn(CO)3(SR)(Ph2PCH2CH2PPh22-P,P′) for R = Ph, C6F5, m-NH2C6H4, p-NH2C6H4, and HSCH2CH2 and fac-Mn(CO)3(SR)(H2NCH2CH2NH22-N,N′) for R = Ph and C6F5. Upon reaction of tricarbonyl-η5-pentadienylmanganese with ethylenediamine a dinuclear complex [fac-Mn(CO)3(μ-H2NCH2CH2NH-κ2-N,N′)]2 was formed wherein the diaminyl ligand functions in the capacity of chelating and bridging ligand.  相似文献   

15.
Reactions of substituted pyridylalkanol 6-CH3PyCH2CH(OH)R (R = Ph (L1H), R = 4-CH3C6H4 (L2H), R = 4-OCH3C6H4 (L3H), R = 4-ClC6H4 (L4H), R = 4-BrC6H4 (L5H), R = 4-CF3C6H4 (L6H)) with Ru3(CO)12 in refluxing tetrahydrofuran afforded the corresponding ruthenium carbonyl complexes [6-CH3PyCH2CHRO]2Ru3(CO)8 (R = Ph ( 1a ), R = 4-CH3C6H4 ( 1b ), R = 4-OCH3C6H4 ( 1c ), R = 4-ClC6H4 ( 1d ), R = 4-BrC6H4 ( 1e ), R = 4-CF3C6H4 ( 1f )) in good yields. These ruthenium complexes were well characterized using elemental analysis and Fourier transform infrared and NMR spectroscopies. Furthermore, their crystal structures were determined using single-crystal X-ray diffraction analysis. Complexes 1a – 1f were found to be highly active toward oxidation of a wide range of primary and secondary alcohols to corresponding aldehydes and ketones within 5 minutes in the presence of N-methylmorpholine-N-oxide as oxidant.  相似文献   

16.
The reactions of PhCboSeNa (Cbo = o-C2B10H10), prepared by reductive cleavage of Se-Se bond in (PhCboSe)2 by NaBH4 in methanol, with Na2PdCl4, MCl2(PR3)2 and [M2Cl2(μ-Cl)2(PR3)2] afforded a variety of complexes, viz., [Pd(SeCboPh)Cl] (1), [M(SeCboPh)2(PR3)2], [M2Cl2(μ-SeCboPh)(μ-Cl)(PR3)2] (M = Pd, Pt) and [Pd2Cl(SeCb0Ph)(μ-Cl)(μ-SeCboPh)(PEt3)2] (7) have been isolated. These complexes were characterized by elemental analyses and NMR (1H, 31P, 77Se, 195Pt) spectroscopy. The structures of [Pd(SeCboPh)2(PEt3)2] (2), [Pt(SeCboPh)2(PMe2Ph)2] (3), [Pd2Cl2(μ-SeCboPh)(μ-Cl)(PMe2Ph)2] (5) and [Pd2Cl(SeCboPh)(μ-Cl)(μ-SeCboPh)(PEt3)2] (7) were established by X-ray crystallography. The latter represents the first example of asymmetric coordination of selenolate ligands in binuclear bis chalcogenolate complexes of palladium and platinum. Thermolysis of [Pd(SeCboPh)2(PEt3)2] (2) in HDA (hexadecylamine) at 330 °C gave nano-crystals of Pd17Se15.  相似文献   

17.
The reactions of a series of 5-alkyl-2-thiophenedithiocarboxylates with nickel(II) chloride afforded two types of complexes, blue nickel(II) complexes with two terminal dithiocarboxylate ligands, [Ni(S2CTR)2] and violet nickel(II) complexes with perthio- and dithiocarboxylate ligands, [Ni(S2CTR)(S3CTR)] (where T = 2,5-disubstituted thiophene, R = CnH2n+1, n = 4, 6, 8, 12, 16). The blue monomers are preferred for the shorter chains (C4 and C6) and the violet compounds form exclusively for the longer chains (C8, C12, and C16) in the alkylthiophene complexes. In addition to the above series, [Ni(S2CTCH3)2], was prepared in a one-pot reaction in THF and both the blue and violet products were isolated. It was possible to convert the blue complexes [Ni(S2CTR)2] (R = butyl, hexyl) into the corresponding violet complexes [Ni(S2CTR)(S3CTR)] after stirring in THF solutions for prolonged periods of time. Liquid-crystalline properties of these complexes were examined by DSC and POM. The violet complexes with C8 and C12 alkyl chains showed liquid-crystalline properties.  相似文献   

18.
A series of 18-electron alkylruthenium complexes, RuR[κ2(N,N′)-(S,S)-R′SO2NCHPhCHPhNH2](η6-arene) (Ph = C6H5, R′ = p-CH3C6H4 and CH3), bearing a N-sulfonylated diamine ligand was synthesized from the reaction of RuCl[κ2(N, N′)-(S,S)-R′SO2NCHPhCHPhNH2](η6-arene) with alkylzinc reagents, in which transmetalation proceeded smoothly to give the desired alkyl complexes in good yield and selectivity. Although the isolable amine Ru complexes bearing functionalized alkyl ligands were thermally stable, the simple methyl and ethyl Ru complexes underwent intramolecular deprotonation from NH protons to give the amido Ru complexes with release of the alkanes. The reactivity of the alkyl Ru complexes is highly affected by the structures of the arene ligands.  相似文献   

19.
The dimanganese hydride complexes [Mn2(μ-H)2(CO)6(μ-L2)] [L2 = (EtO)2POP(OEt)2 (tedip), Ph2PCH2PPh2 (dppm)] react with primary and secondary silanes H2SiPhR (R = Ph, Me, H) to give the corresponding derivatives [Mn2(μ-H2SiPhR)(CO)6(μ-L2)] having a silane molecule displaying a relatively unusual μ-κ22 coordination mode (averaged values are ca. Mn-H = 1.59 Å, H-Si = 1.69 Å and Mn-Si = 2.381 Å, when R = Ph and L2 = tedip). These complexes display in solution cis and/or trans arrangement of the bridging silane relative to the diphosphorus ligands (and facial and/or meridional arrangements of the corresponding carbonyl ligands), depending on the bridging groups. The novel unsaturated dihydride [Mn2(μ-H)2(CO)6(μ-dmpm)] (dmpm = Me2PCH2PMe2) has been prepared through the reaction of [Mn2(μ-Cl)2(μ-dmpm)(CO)6] and 5 equiv of Li[BH2Me2] in tetrahydrofuran followed by addition of water. The dihydride complexes [Mn2(μ-H)2(CO)6(μ-L2)] (L2 = tedip, dppm, dmpm) react with HSnPh3 to give different mixtures of products strongly dependent on the particular reaction conditions. We have thus been able to isolate and characterize five new types of dimanganese-tin derivatives: [Mn2(μ-SnPh2)2(CO)6(μ-L2)], [Mn2(μ-H)(μ-Ph2SnO(H)SnPh2)(CO)6(μ-L2)] (average values are Mn-Sn = 2.54 Å, Sn-O = 2.11 Å, when L2 = tedip), [Mn2(μ-H)(μ-κ12-HSnPh2)(CO)6(μ-L2)], [Mn2(μ-H)(μ-κ11-O(H)SnPh2)(CO)6(μ-L2)], and [Mn2(μ-H)(SnPh3)(CO)7(μ-L2)] (Mn-Mn = 3.237(1) Å, Mn-Sn = 2.642(1) Å, when L2 = dppm).  相似文献   

20.
The reaction of tricarbonylpentadienylmanganese with aryl mercaptans in the presence of phosphines or phosphites afforded dinuclear complexes, [Mn2(CO)4(μ-CO)(μ-SR)2(PR′3)2]; R = Ph for PR′3 = PPh3, PMe3, P(OMe)3, P(OEt)3, PMePh2 and R = m-, p-NH2C6H4S-, for PR′3 = PPh3 in one pot synthesis. Two reaction routes were proposed for the formation of the dinuclear complexes depending on the relative basicity of the sulfur vs. phosphine ligands. Characterization of the complexes was effected in solution and, for [Mn2(CO)4(μ-CO)(μ-SPh)2(PPh3)2], [Mn2(CO)4(μ-CO)(μ-SPh)2(P(OEt)3)2], and [Mn2(CO)4(μ-CO)(μ-SPh)2(PMe3)2], by X-ray crystallographic analysis.  相似文献   

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