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1.
Bis(cyclopentadienyl)methane-bridged Dinuclear Complexes. VIII. Dinuclear Cobalt Complexes with the Dianion of Bis(cyclopentadienyl)methane and Bis(tetramethylcyclopentadienyl)dimethylsilane as Bridging Ligands The dinuclear cobalt complex [CH2(C5H4)2][Co(CO)2]2 ( 4 ) which is obtained from [Co(CO)4I] ( 2 ) and Li2[CH2(C5H4)2] ( 3 ) in 75% yield reacts with PMe3, PiPr3, P2Me4, Me2PCH2CH2PMe2 and (EtO)2POP(OEt)2, to the compounds 5–9 substituting one CO ligand per cobalt atom. Oxidative addition of CH3I to [CH2(C5H4)2][Co(CO)(PMe3)]2 ( 5 ) leads to the formation of the dinuclear cobalt(III) complex [CH2(C5H4)2][Co(COCH3)(PMe3)I]2 ( 11 ). The reaction of 4 with iodide generates [CH2(C5H4)2][Co(CO)I2]2 ( 12 ) which with PMe3, P(OMe)3, P(OiPr)3, and CNMe reacts under CO substitution to [CH2(C5H4)2][Co(L)I2]2 ( 13–16 ) and with PMe2H to {[CH2(C5H4)2][Co(PMe2H)3]2}I4 ( 17 ). The electrophilic addition reactions of NH4PF6 and CH3I to [CH2(C5H4)2][Co(PMe3)2]2 ( 20 ) produce the complex salts {[CH2(C5H4)2][CoR(PMe3)2]2}X2 ( 21 : R = H; 22 : R = CH3). From 22a (X = I) and LiCH3 the dinuclear tetramethyldicobalt compound [CH2(C5H4)2] · [Co(CH3)2(PMe3)]2 ( 23 ) is obtained which further reacts, via the intermediate 24 , to the chiral complex {[CH2(C5H4)2] · [CoCH3(PMe3)P(OMe)3]2}(PF6)2 ( 25 ). The reaction of 20 with C2(CN)4 and E- or Z-C2H2(CO2Me)2 gives the olefin(trimethylphosphine) cobalt(I) derivatives 26 und 27 . The synthesis of the dinuclear compounds 31–38 with [Me2Si(C5Me4)2]2? as the bridging unit is also described.  相似文献   

2.
The complexes C5H5Rh(PMe3)C2H3R′ (R′  H, Me, Ph) and C5H5Rh(PR3)C2H4(PR3  PMe2Ph, PPri3) are prepared by reaction of[PMe3(C2H3R/t')RhCl]2 or [PR3(C2H4)RhCl]2 and TlC5H5, respectively. They react with HBF4 in ether/propionic anhydride to form the BF4 salts of the hydrido(olefin)rhodium cations [C5H5RhH(C2H3R′)PR3]+(R  Me; R′  H, Me and R  Pri; R′  H). From C5H5Rh(PMe3)C2H3Ph and CF3COOH/NH4PF6 the η3-benzyl complex [C5H5Rh(PMe3)(η3-CH3CHC6H5)]PF6 is obtained. The reversibility of the protonation reactions is demonstrated by temperature-dependent NMR spectra and by deuteration experiments. The complexes C5H5Rh(PMe3)C2H3R′ (R′  H, Ph) and C5H5Rh(PMe2Ph)C2H4 react with CH3I in ether to give the salts [C5H5RhCH3(C2H3R′)PR3]I which in THF or CH3NO2 yield the neutral compounds C5H5RhCH3(PR3)I.  相似文献   

3.
The hydrido-bridged dinuclear complex [(C5H5CO)2(μ-PMe2)2(μ-H)]BF4 (I) reacts with C2(CO2Me)2 to produce a mixture of (C5H5Co)2[μ-η4-Me2PC(CO2Me)C(CO2Me)PMe2] (II) and [(C5H5Co)2(μ-PMe2)(μ-η4-Me2PC(CO2Me)-CHC(OMe)O)]BF4 (III). The X-ray structural analysis of III reveals that besides a dimethylphosphido bridge the cation contains a substituted vinyldimethylphosphine ligand which behaves as a 6-electron donor group and is coordinated via phosphorus and oxygen to the first cobalt and via the CC bond the second cobalt atom. The reactions of I with HC2CO2Me and CH3C2CO2Me also give mixtures of products which contain the neutral component, (C5H5Co)2[μ-η4-Me2PCRC(CO2Me)PMe2] (IV: R  H; VII: R  CH3), i.e., the structural analogue of II. The ionic products V, VI (obtained from HC2CO2Me) and VIII, IX (obtained from CH3C2CO2Me) have been characterized by IR and NMR spectroscopy. {(C5H5Co)2[μ-η4-PMe2C(CH3)C(CO2Me)PMe2](μ-H)}BF4 (VIII) has independently been prepared by treatment of VII with HBF4.  相似文献   

4.
The cyclopentadienylcobalt(I) compounds C5H5Co(PMe3)P(OR)3 (R = Me, Et, Pri) and C5H5Co(C2H4)L (L = PMe3, P(OMe)3, CO) are prepared by ligand substitution starting from C5H5Co(PMe3)2 and C5H5Co(C2H4)2. Whereas the reaction of C5H5Co(PMe3)P(OMe)3 with CH2Br2 mainly gives [C5H5CoBr(PMe3)P(OMe)3]Br, the dihalogenocobalt(III) complexes C5H5CoX2(PMe3) (X = Br, I) are obtained from C5H5Co(CO)PMe3 and CH2X2. Treatment of C5H5Co(CO)PMe3 or C5H5Co(C2H4)PMe3 with CH2ClI at low temperatures produces a mixture of C5H5CoCH2Cl(PMe3)I and C5H5CoCl(PMe3)I, which can be separated due to their different solubilities. The same reaction in the presence of ligand L gives the carbenoidcobalt(III) compounds [C5H5CoCH2Cl(PMe3)L]PF6 in nearly quantitative yields. If NEt3 is used as the Lewis base, the ylide complexes [C5H5Co(CH2PMe3)(PMe3)X]PF6 (X = Br, I) are obtained. The PF6 salts of the dications [C5H5Co(CH2PMe3)(PMe3)L]2+ (L = PMe3, P(OMe)3, CNMe) and [C5H5Co(CH2PMe3)(P(OMe)3)2]2+ are prepared either from [C5H5Co(CH2PMe3)(PMe3)X]+ and L, or more directly from C5H5Co(CO)PMe3, CH2X2 and PMe3 or P(OMe)3, respectively. The synthesis of C5H5CoCH2OMe(PMe3)I is also described.  相似文献   

5.
C5H5Co(PMe3)2 (I) reacts with CSSe to give C5H5Co(η2-CSSe)PMe3 (IV) and C5H5Co(CS)PMe3 (V). The thiocarbonyl complex V is formed in an almost quantitative yield by Se abstraction from IV and PPh3. The corresponding compounds C5H5Co(CS)PMe2Ph (VII) and C5H5Co(CS)[P(OMe)3] (VIII) are obtained as the main products directly from CSSe and C5H5Co(PMe2Ph)2 or C5H5Co[P(OMe)3]2. In the reaction of C5H5Co(PR3)2 (PR3 = PMe3, PMe2Ph) with CSe2, the carbon diselenide complexes C5H5Co(η2-CSe2)PMe3 (XI) and C5H5Co(η2-CSe2)PMe2Ph (XIV) are formed. XI reacts with PPh3 to give C5H5Co(CSe)PMe3 (XII). Cyclopentadienylcobalt compounds containing CSSe22?, CSe32? and C2Se42? as ligands are isolated as side products in the; reactions of C5H5Co(PR3)2 and C5H5Co(CO)PR3 (PR3 = PMe3, PMe2Ph) with CSSe and CSe2, respectively. Displacement of ethylene from C5H5Rh(C2H4)PMe3 by CSSe yields the complex C5H5Rh(η2-CSSe)PMe3 (XVIII) which reacts with PPh3 to give C5H5Rh(CS)PMe3 (XIX) and with excess CSSe to give C5H5RhC2S2Se2(PMe3) (XX). Besides small amounts of C5H5Rh(η2CSSe)PMe2Ph (XXI), the corresponding metallaheterocycle C5H5RhC2S2Se2(PMe2Ph) (XXII) is formed as the main product from C5H5Rh(C2H4)PMe2Ph and CSSe.  相似文献   

6.
The dinuclear cobalt complex [CH2(C5H4)2][Co(PMe3)2]2 (2), which is prepared from CoCl(PMe3)3 and [CH2(C5H4)2]Li2, reacts with NH4PF6 and CH3I to form the protonated and methylated dications {[CH2(C5H4)2][CoR(PMe3)2]2}2+ (R = H, CH3). Treatment of {[CH2(C5H4)2][CoCH3(PMe3)2]2}I2 (4) with LiCH3 affords the neutral compound [CH2(C5H4)2][Co(CH3)2(PMe3)]2 (5). Ligand substitution of [CH2(C5H4)2][Co(CO)2]2 (6) with P2Me4 and 1,2-C2H4(PMe2)2(dmpe) gives the doubly-bridged complexes [CH2(C5H4)2][Co2(CO)2(μ-P2Me4)] (7) and [CH2(C5H4)2][Co2(CO)2(μ-dmpe)] (8), respectively. Similarly, [CH2(C5H4)2][Co-(CO)(PMe3)]2 (9) is obtained from the reaction of 6 with PMe3. Oxidation of 6 with iodine gives [CH2(C5H4)2][Co(CO)I2]2 (11) which is transformed via {[CH2(C5H4)2][Co(PMe2H)3]2}I4 (12) into the triply-bridged cobalt(II) complex [CH2(C5H4)2][CO2(μ-PMe2)2] (13).  相似文献   

7.
Basic Metals. XIV. Synthesis and Crystal Structure of C5H5(PMe3)CoS5: A New Metallapentathia Heterocycle The dinuclear complex C5H5(PMe3)Co(μ-CO)2Mn(CO)C5H4Me ( 3 ) reacts with stoi-chiometric amounts of S8 to form C5H5(PMe3)CoS5 ( 4 ) in practically quantitative yields. The cobalt-apentathia heterocycle 4 is also obtained by the reaction of C5H5(PMe3)Co(h2-CS2) ( 5 ) with S8. Crystals of 4 are monoclinio with a = 8.467(3) Å, b = 12.128(4) Å, c = 14.210(4) Å and Å = 102.20(2)°. The chair form of the six-membered CoS5 ring corresponds to that of the compounds (C5H5)2TiS5 and (C5H5)2VS5. In 4 , the cyclopentadienyl ligand occupies the axial and the trimethylphosphine group the equatorial position.  相似文献   

8.
The complex [C5H5RhH(C2H4)PMe3]BF4 (I) reacts with NaF and NaCN by deprotonation to give C5H5Rh(PMe3)C2H4 but with NaCl, NaBr and NaI the ethylrhodium compounds C5H5RhC2H5(PMe3)X (II–IV) are obtained. The reactions of I with CO and PPri3 yield the BF4 salts of the cations [C5H5RhH(CO)PMe3]+ and [C5H5RhH(PPri3)PMe3]+ (V, VI), respectively, from which the uncharged complexes C5H5Rh(CO)PMe3 (VII) and C5H5Rh(PPRi3)PMe3 (VIII) are prepared. The carbonyl compound VII is also accessible either from C5H5Rh(CO)2 and PMe3 or from C5H5Rh(PMe3)2 and CO. The reaction of I with ethylene leads to the BF4 salt of the cation [C5H5RhC2H5(PMe3)C2H4]+ (X) which on treatment with PMe3 forms the complex [C5H5RhC2H5(PMe3)C2H4PMe3]BF4 (XI). The compound [C5H5RhH(C2H4)PPri3]BF4 (XII) reacts with NaI by insertion to yield C5H5RhC2H5(PPri3)I (XIII) whereas with PPri3 the salt [C5H5RhH(PPri3)2]BF4 (XIV) is produced. The bis(triisopropylphosphine) complex C5H5Rh(PPri3)2 (XVI) is obtained from XIV and NaH.  相似文献   

9.
10.
Multifaceted Coordination Chemistry of Vanadium(V): Substitution, Rearrangement Reactions, and Condensation Reactions of Oxovanadium(V) Complexes of the Tripodal Oxygen Ligand LOMe? = [η5‐(C5H5)Co{P(OMe)2(O)}3]? The octahedral oxovanadium(V) complex [V(O)F2LOMe] of the tripodal oxygen ligand LOMe? = [η5‐(C5H5)Co{P(OMe)2(O)}3]? reacts with alcohols and phenol with substitution of one fluoride ligand to form alkoxo complexes [V(O)F(OR)LOMe], R = Me, Et, i‐Prop, Ph. In the presence of water, however, both fluoride ions are substituted and a complex with the composition VO2LOMe can be isolated. The crystal structure shows that the oxo‐bridged trimer [{V(O)(LOMe)O}3] was synthesized. In the presence of BF3 the fluoride ligand in the alkoxo‐complex [V(O)F(OEt)LOMe] can be exchanged for pyridine to yield [V(O)(OEt)pyLOMe]BF4. Analogous attempts to exchange the fluoride ligand for tetrahydrofuran and acetonitrile induces a rearrangement reaction that leads to the vanadium complex [V(O)(LOMe)2]BF4. The crystal structure of this compound has been determined. Its 1H and 31P‐NMR spectra show that it is a highly fluxional vanadium complex at ambient temperature in solution. The two tripodal ligands LOMe? coordinate the vanadium centre as bidentate or tridentate ligands. The exchange bidentate/tridentate becomes slow on the NMR time scale below about 200 K.  相似文献   

11.
[(C5H5Co)2(μ-PMe2)2(μ-H)]BF4 ([II]BF4) reacts with C2(CO2Me)2 to give the products III and IV. The ionic compound III which formally is a 11 adduct of [II]BF4 and C2(CO2Me)2 has been characterized by X-ray structure analysis. III contains the group O=C(OMe)CH=C(CO2Me)PMe2 as a 6-electron donor ligand chelated to a cobalt atom and π-bonded to the other cobalt atom. Complex IV is a neutral compound which also can be obtained from [C5H5Co(μ-PMe2)]2 (I) and C2(CO2Me)2.  相似文献   

12.
The bis(μ-dimethylphosphido)dicobalt complex [C5H5Co(μ-PMe2)]2 (II) has been prepared from Co(C5H5 and PMe2H on almost quantitative yield. It has also been made by reduction of [C5H5Co(PMe2H)3]I2 (IV) with NaH and from the reaction of [C5H5(PMe3)Co(μ-CO)2Mn(CO)C5H4Me] with PMe2H. Protonation of II with CF3CO3H in the presence of NH4PF6 produces the PF6? salt of the (μ-hydrido)dicobalt cation [(C5H5Co)2(μ-H)(μ-PMe2)2]+ (V) which reacts with aqueous NaOH to give II. Similar treatment of [C5H5Co(μ-SMe]2 with CF3CO2H/NH4PF6 leads to the formation of [(C5H5Co)2(μ-SMe)3]PF6 (VI). The nucleophilic character of complex II has also been demonstrated in the reaction with SO2, which gives [(C5H5Co)2 (μ-PMe2)2(μ-SO2)] (VII). The crystal and molecular structures of II, the corresponding bis(μ-diphenylphosphido) compound [C5H5Co(μ-PPh2)]2 (III) and the BPh4? salt of V have been determined. In both neutral complexes the Co2P2 cores are similarly puckered, as reflected in the dihedral angle between the CoP2 and P2Co′ planes of 108.1 and 105.0° for R = Me and Ph, respectively. The CoCo bond length and the PP interatomic separations are essentially identical for both dimers. The CoCo bond length in V, 2.517(1) Å, is lower than that in II, 2.542(2) Å. The only obvious structural variation between the unprotonated and the protonated species is the large difference in the degree of canting of the C5H5 rings with respect to each other. The angles between the C5(ring)-centroid and the CoCo line are ca. 150 and 167° in II and V, respectively, which reflects the influence of the bridging hydride ligand in the cationic complex.  相似文献   

13.
《Polyhedron》1986,5(8):1363-1370
Co-condensation of rhenium atoms with a benzene-trimethylphosphine mixture gives the dimer [Re(ν-C6H6)(PMe3)2]2 which is a precursor to the new compounds Re(η-C6H6)(PMe3)2R (R = H, Cl, I, Me, Et, CHCH2 or Ph), [Re(η-C6H6)(PMe3)2X2]BF4 (X2 = H2 or HI), [Re(η-C6H6)(PMe3)2H2][BF4]2, and [Re(η-C6H6)(PMe3)2L]BF4 (L = η-C2H4 or CO). Co-condensation of manganese atoms with benzene-trimethylphosphine gives Mn(η-C6H6)(PMe3)2H.  相似文献   

14.
The reaction between [{Ru(CO)Cl2(PMe2Ph)2}2] and SnBu3(C5H7) in chloroform yields the η3-pentadienyl complex [Ru(CO)Cl(η3-C5H7)(PMe2Ph)2]. The 1H NMR spectra are reported and discussed.  相似文献   

15.
The two‐step one‐pot oxidative decarbonylation of [Fe2(S2C2H4)(CO)4(PMe3)2] ( 1 ) with [FeCp2]PF6, followed by addition of phosphane ligands, led to a series of diferrous dithiolato carbonyls 2 – 6 , containing three or four phosphane ligands. In situ measurements indicate efficient formation of 1 2+ as the initial intermediate of the oxidation of 1 , even when a deficiency of the oxidant was employed. Subsequent addition of PR3 gave rise to [Fe2(S2C2H4)(μ‐CO)(CO)3(PMe3)3]2+ ( 2 ) and [Fe2(S2C2H4)(μ‐CO)(CO)2(PMe3)2(PR3)2]2+ (R=Me 3 , OMe 4 ) as principal products. One terminal CO ligand in these complexes was readily substituted by MeCN, and [Fe2(S2C2H4)(μ‐CO)(CO)2(PMe3)3(MeCN)]2+ ( 5 ) and [Fe2(S2C2H4)(μ‐CO)(CO)(PMe3)4(MeCN)]2+ ( 6 ) were fully characterized. Relevant to the Hred state of the active site of Fe‐only hydrogenases, the unsymmetrical derivatives 5 and 6 feature a semibridging CO ligand trans to a labile coordination site.  相似文献   

16.
The diiron vinyl ether carbyne complex [(C5H5)(CO)Fe]2(μ-CO)- (μ-CCHCHOCH2CH3)+ BF4 (1) reacted with the diiron ethenylidene complex [(C5H5)(CO)Fe]2(μ-CO)(μ-CCH2) (2) to yield the tetrairon complex [(C5H5)2(CO)2Fe2(μ-CO)]2(μ-C5H3+BF4 (3) which was characterized by spectroscopy and by single crystal X-ray diffraction.  相似文献   

17.
Li2[(C5Me4)2CH2] (III), the dilithium salt of the novel permethylated ring-connected [(C5Me4)2CH2]2− dianion, has been prepared from C5Me4H2 (I) via (C5Me4H)2CH2 (II) and subsequent reaction with n-BuLi. III reacts with [Rh(C2H4)(PMe3)Cl]2 to give the dinuclear complex [(C5Me4)2CH2][Rh(C2H4)PMe3]2 (IV) from which on methylation the compounds {[(C5Me4)2CH2][RhCH3(C2H4)PMe3]2} (PF6)2 (V) and [(C5Me4)2CH2][RhCH3(PMe3)I]2 (VI) are obtained. Treatment of IV with excess trifluoroacetic acid leads to the formation of [(C5Me4)2CH2](Rh(PMe3)(OCOCF3)2]2 (VII) which reacts with chelating diphosphines in the presence of NH4PF6 to give the PF6 salts of the doubly-bridged dications {[(C5Me4)2CH2][Rh2(PMe3)2(OCOCF3)2(μ-P-P)]}2+ (PP = dppm, dppe, dppb) (IX–XI). The reaction of III with [Rh(CO)2Cl]2 produces a mixture of the dinuclear complexes [(C5Me4)2CH2][Rh(CO)2]2 (XII) and [(C5Me4)2CH2][Rh2(μ-CO)2] (XIII) which are easily interconverted under mild conditions.  相似文献   

18.
Reaction of the η2(C,S)-coordinated thioketene cobalt complex [Co(C11H18S)-(PMe3(C5H5)] (2a) with the electrophils [Mn(CO)2(THF)(C5H5] and [Cr(CO)5(THF)] gives the dinuclear thioketene complexes (4) with two different metal atoms in the molecule. The structure of the cobalt manganese compound was determined by X-ray diffraction. Protonation of the mononuclear thioketene complexes 2 give novel cationic η2-bonded thioacyl compounds [Co(η2-RCS)-(PMe3(C5H5)]+ (9), as confirmed by X-ray analysis.  相似文献   

19.
The reduction of trans-RuCl2(PMe3)4 with Na/Hg and of trans-OsCl2(PMe3)4 with sodium in the presence of catalytic amounts of naphthalene gives the complexes RuH(η2-CH2PMe2)(PMe3)3 (III) and OsH(η2-CH2PMe2PMe2), (IV) in good yields. An equilibrium with the metal(0) isomers [M(PMe3)4] cannot be detected by NMR spectroscopy. III and IV react with dihalomethanes CH2X2 (X = Cl, Br, I) and CH3I to form mixtures of the dimethylphosphinomethanide complexes MX(η2-CH2PMe2)(PMe3)3 and the compounds MX2(PMe3)4. The reactions of III and IV with the Brönsted acids HCl, HBr, CF3CO2H and HC2Ph lead (with exception of M = Ru and X = C2Ph) to the complexes cis-MX2(PMe3)4. The hydrolysis of IV gives the hydrido(hydroxy) compound cis-OsH(OH)(PMe3)4, which has been characterized by 1H, 31P NMR and mass spectroscopy. The synthesis of the complex cis-Os(CH3)2(PMe3)4 is also described; the conversion into the ethylene(hydrido)metal cation [OsH(C2H4)(PMe3)4]+ failed.  相似文献   

20.
The interaction of azidotrimethylsilane with mer-CoMe3(PMe3)3, fac-RhMe3(PMe3)3, fac-IrMe3(PMe2Ph)3, cis-RuMe2(PMe3)4 and (η5-C5H5)2ZrMe2 gives tetramethylsilane and, respectively, the azido compounds MMe2(N3)(PMe3)3, M = Co, Rh, IrMe2(N3)(PMe2Ph)3, cis-Ru(N3)2(PMe3)4 and (η5-C5H5)2ZrMe(N3). The crystal structures of CoMe2(N3)(PMe3)3 and of the derived complex Co(N3(CO)2(PMe3)2 have been determined by X-ray diffraction.The dimethyl cobalt(III) compound has an octahedral structure with a mer arrangement of the three PMe3 groups. The CoIII-N distance is rather long, at 2.071(4) Å. The cobalt(I) carbonyl compound has a trigonal bypyramidal structure with the two phosphines occupying the axial sites. The CoI-N distance is 2.03(1) Å.The interaction of PhN3 with (η5-C5H5)2ZrR2, R = Me, Ph, gives the 1,3-triazenido complexes (η5-C5H5)2ZrR(RNNNPh) while mer-CoMe3(PMe3)3 and p-MeC6H4N3 react to give CoMe2(MeNNNp-tol)(PMe3)2. In all three cases the triazenido group appears to be bidentate.  相似文献   

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