Your email was sent successfully. Check your inbox.

An error occurred while sending the email. Please try again.

Proceed reservation?

Export
  • 1
    ISSN: 1434-1948
    Keywords: Rhodium ; Carbenoide metal complexes ; Formaldehyde complexes ; Thioformaldehyde complexes ; Cyclopentadienyl complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The acetoxymethyl rhodium compounds [(η5-C5R5)Rh(CH2OAc)(L)I] (4, 13-16) which were prepared from the chloromethyl derivatives [(η5-C5R5)Rh(CH2Cl)(L)I] and sodium acetate in benzene/acetic acid as solvent, reacted with AgPF6 to give the chelate complexes [(η5-C5R5)Rh{ĸ2-C,O-CH2OC(Me)O}(L)]PF6 (19-23) in excellent yields. Treatment of these complexes with KOH in methanol led to the elimination of the acetyl group and to the formation of the formaldehyde compounds [(η5-C5R5)Rh(η2-CH2O)(L)] (24-27). The related thioformaldehyde complexes [(η5-C5Me5)Rh(η2-CH2S)(L)] (46, 47) and [(η5-C5H5)Rh(η2-CH2S)(PMe3)] (50) were obtained on a similar route. Studies on the reactivity of the formaldehyde derivatives revealed that the Rh-CH2O bond is rather labile and the CH2O ligand easily converted to a CO group.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Signatur Availability
    BibTip Others were also interested in ...
  • 2
    ISSN: 1434-1948
    Keywords: Rhodium ; Alkyne complexes ; Alkynyl(hydrido) complexes ; Vinylidene complexes ; Dendrimer-like structure ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dimer [RhClL2]2 (1; L = PiPr3) reacts with 1,3,5-C6H3(C≡CH)3 to give in the initial step the tris(alkyne)trirhodium compound 2, which rearranges in toluene at 60 °C to yield the isomeric tris(vinylidene) complex 3. Treatment of either 2 or 3 with pyridine affords the trinuclear tris(alkynyl)trihydridorhodium(III) complex 4. The trisilyl derivative 1,3,5-C6H3(C≡CSiMe3)3 reacts with 1 to form the mononuclear compound 5, in which only one of the C≡C bonds is coordinated to Rh. The diynes 1,3- and 1,2-C6H4(C≡CH)2 behave analogously to 1,3,5-C6H3(C≡CH)3 and upon treatment with 1 yield initially the bis(alkyne)dirhodium complexes 6 and 7 and subsequently the bis(vinylidene)dirhodium isomers 8 and 9. The reactions of 1,2-, 1,3-, and 1,4-C6H4(C≡CSiMe3)2 with 1 take a similar course and give the bis(alkyne) and bis(vinylidene) compounds 10-12 and 13-15, respectively. In the same way, the dinuclear bis(alkyne) and bis(vinylidene) complexes 16 and 17 have been prepared from 1 and the naphthalene derivative 1,5-C10H6(C≡CH)2. The molecular structures of 17 and of the dendrimer-like Rh3 compound 3 have been determined by X-ray crystallography.
    Type of Medium: Electronic Resource
    Signatur Availability
    BibTip Others were also interested in ...
  • 3
    ISSN: 1434-1948
    Keywords: Rhodium ; Ketone complexes ; Vinylidene complexes ; Allenylidene complexes ; Ligand substitution reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complex [Rh(acetone)2(C8H14)2]PF6 (2), which is prepared from [RhCl(C8H14)2]2 and AgPF6 in acetone, reacts with PiPr3 to afford the PF6 salt 3 of the cation [Rh(acetone)2(PiPr3)2]+ containing the ketone and phosphane ligands in cis dispositions. Treatment of 3 with MeC≡CPh leads to the displacement of one acetone ligand and the formation of the corresponding π-alkyne complex 4. In contrast, from 3 and terminal alkynes such as HC≡CC6H4-4-Me or HC≡CCPh2OH the cationic vinylidenerhodium(I) compounds 5 and 6 are obtained. The latter, with C=CHCPh2OH as the ligand, is rather labile and even at room temperature eliminates water to give the cationic four-coordinate rhodium allenylidene 7. The molecular structure of this compound has been determined by X-ray crystallography. In the presence of pyridine or ammonia, the acetone ligand of 5 and 7 is readily displaced and the substitution products 8-10 are formed almost quantitatively. Anions such as acetate or hydroxide also displace the ketone unit of 7 and yield the neutral allenylidenerhodium(I) complexes trans-[RhX(=C=C=CPh2)(PiPr3)2] with × = OAc (11) and OH (12).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Signatur Availability
    BibTip Others were also interested in ...
  • 4
    ISSN: 0009-2940
    Keywords: Rhodium complexes ; Molecular structure ; square-planar ; Hydrogenation reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis(triisopropylphosphane)rhodium Dichloride: Formation and StructureThe mononuclear rhodium(II) complex trans-[RhCl2(PiPr3)2] (4) has been obtained from [RhCl(PiPr3)2]n (3) and CCl4. The X-ray structural analysis of 4 reveals a square-planar coordination at the metal center. Reaction of 4 with H2 leads to the formation of the monohydrido compound [RhHCl2(PiPr3)2] (7) which on further treatment with H2 in the presence of Na[N(SiMe3)2] gives the dihydride [RhH2Cl(PiPr3)2] (8). Complex 7 has also been prepared from 3 and HCl.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Signatur Availability
    BibTip Others were also interested in ...
  • 5
    ISSN: 0009-2940
    Keywords: Phospha- and arsaalkene rhodium complexes ; Metalla heterocycle containing RhAs3 ; Rhodium complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: CH2=PPH and CH2=AsPh as Ligands Coordinated to Rhodium. Crystal and Molecular Structure of C5Me5Rh(η2-CH2PPh)(CO) and C5Me5(CO)Rh(AsPh)3C5Me5RhCH2I(CO)I (1) reacts with excess LiPHPh or LiAsHPh to give the complexes C5Me5Rh(η2-CH2EPh)(CO) (2: E = P; 3: E = As). The C—P bond length of the coordinated phosphaalkene in 2 is 174.0(4) pm and thus ca. 10 pm shorter than that of a C—P single bond. On standing in solution, the new heterocycle C5Me5(CO)Rh(AsPh)3 (4) is formed from 3. The X-ray analysis of 4 shows that the bonding distances and angles in the central nonplanar RhAs3 four-membered ring are very similar to thos in cyclo-(AsCF3)4.
    Notes: C5Me5RhCH2I(CO)I (1) reagiert mit überschüssigem LiPHPh oder LiAsHPh zu den Komplexen C5Me5Rh(η2-CH2EPh)(CO) (2: E = P; 3: E = As). Der C—P-Abstand des koordinierten Phosphaalkens in 2 ist mit 174.0(4) pm um ca. 10 pm kürzer als der einer C—P-Einfachbindung. Beim Stehenlassen in Lösung entsteht aus 3 teilweise der Heterocyclus C5Me5(CO)Rh(AsPh)3 (4), von dem die Struktur bestimmt wurde. Die Bindungsabstände und -winkel in dem zentralen, nicht planaren RhAs3-Vierring sind denen in cyclo-(AsCF3)4 sehr ähnlich.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Signatur Availability
    BibTip Others were also interested in ...
  • 6
    ISSN: 0009-2940
    Keywords: Cyclopentadienyl anion, substituted ; Cobalt complexes ; Rhodium complexes ; Iridium complexes ; Bis(cyclopentadienyl)methane dianion as bridging ligand ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis(cyclopentadienyl)methane-bridged Dinuclear Complexes, V[1]. - Heteronuclear Co/Rh-, Co/Ir-, Rh/Ir-, and Ti/Ir Complexes with the Bis(cyclopentadienyl)methane Dianion as Bridging Ligand*The lithium and sodium salts of the [C5H5CH2C5H4]- anion, 1 and 2, react with [Co(CO)4I], [Rh(CO)2Cl]2, and [Ir(CO)3Cl]n to give predominantly the mononuclear complexes [(C5H5-CH2C5H4)M(CO)2] (3, 5, 7) together with small amounts of the dinuclear compounds [CH2(C5H4)2][M(CO)2]2 (4, 6, 8). The 1H- and 13C-NMR spectra of 3, 5, and 7 prove that the CH2C5H5 substituent is linked to the π-bonded ring in two isomeric forms. Metalation of 5 and 7 with nBuLi affords the lithiated derivatives 9 and 10 from which on reaction with [Co(CO)4I], [Rh(CO)2Cl]2, and [C5H5TiCl3] the heteronuclear complexes [CH2(C5H4)2][M(CO)2][M′(CO)2] (11-13) and [CH2(C5H4)2]-[Ir(CO)2][C5H5TiCl2] (17) are obtained. Photolysis of 11 and 12 leads almost quantitatively to the formation of the CO-bridged compounds [CH2(C5H4)2][M(CO)(μ-CO)M′(CO)] (14, 15). According to an X-ray crystal structure analysis the Co/Rh complex 14 is isostructural to [CH2(C5H4)2][Rh2(CO)2(μ-CO)] (16).
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Signatur Availability
    BibTip Others were also interested in ...
  • 7
    ISSN: 0009-2940
    Keywords: Dinuclear rhodium and iridium complexes ; Bis(cyclopentadienyl)methane dianion as bridging ligand ; Substitution and bridge-splitting reactions ; Rhodium complexes ; Iridium complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis(cyclopentadienyl)methane-Bridged Dinuclear Complexes, IV[1].  -  Synthesis, Structure, and Reactivity of Dinuclear Rhodium and Iridium Complexes in the Oxidation State +I and +III with the Bis(cyclopentadienyl)methane Dianion as Bridging LigandThe rhodium compounds [CH2(C5H4)2][Rh(L)(C2H4)]2 (2, 4) were prepared from [RhCl(L)(C2H4)]2 (1, 3) and CH2(C5H4)2Li2 in 92 and 73% yield, respectively. The reaction of 4 with Cl2, Br2, and I2 led to the almost quantitative formation of the dihalogeno derivatives [CH2(C5H4)2][RhX2(PiPr3)]2 (6-8), which on treatment with excess NaBH4 and methanol gave the dihydride [CH2(C5H4)2][RhH2(PiPr3)]2 (10). From [RhCl(C8H14)2]2 (12), PiPr3, and CH2(C5H5)2 the chloro(hydrido)rhodium complex [CH2(C5H4)2][RhH(Cl)(PiPr3)]2 (13) was obtained. Protonation of 10 with CF3CO2H in the presence of NH4PF6 gave the PF6 salt of the hydrido-bridged cation {[CH2(C5H4)2]-[RhH(PiPr3)]2(μ-H)}+ (14) of which the crystal structure was determined. In solution, fluxional behavior of the cation was observed. The dimethyl compound [CH2(C5H4)2][Rh(CH3)2-(PiPr3)]2 (17), prepared from 6, 7, or 8 and LiCH3 or CH3MgI in 80% yield, reacted with CF3CO2H at  -  78° C to give the tri-fluoroacetato derivative 18; this on treatment with P(OMe)3 and dmpe formed the dicationic complexes 19 and 20, respectively. The dinuclear iridium compounds [CH2(C5H4)2]-[Ir(olefin)2]2 (26, 27) and [CH2(C5H4)2][Ir(C8H12)]2 (28) were prepared from [IrCl(L)2]2 (23-25) and CH2(C5H4)2Li2 and used for the synthesis of {[CH2(C5H4)2][IrX2]2}n (29, 30). Compounds 29 and 30 served as starting materials for the preparation of the dinuclear derivatives [CH2(C5H4)2][IrX2(L)]2 (31-34) and {[CH2(C5H4)2][IrBr2]2(μ-dipy)} (35) and finally also for the dihydrido complex [CH2(C5H4)2][IrH2(PiPr3)]2 (36).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Signatur Availability
    BibTip Others were also interested in ...
  • 8
    ISSN: 0009-2940
    Keywords: Rhodium complexes ; Alkyne complexes ; Insertion reactions ; Alkyl isocyanides ; Metallacycles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cyclopentadienyl complexes [C5H5Rh(RC≡CR′)(SbiPr3)] (5-8), which were prepared from trans-[RhCl-(RC≡CR′)(SbiPr3)2] (1-4) and NaC5H5 and which contain a labile Rh-SbiPr3 bond, reacted with CO and CNR″ (R″ = Me, tBu) to give the carbonyl and isocyanide derivatives [C5H5Rh(RC≡CR′)(CO)] (9-11) and [C5H5Rh(RC≡CR′)-(CNR″)] (12-16), respectively. On treatment of 12 (R = R′ = Ph; R″ = Me) with SbiPr3, the metallacyclobutene complex [C5H5Rh{κ2(C,C}-C( = NMe)CPh=CPh}(SbiPr3)] (17) was formed; it reacts with excess CNMe or CNtBu to yield the metallacyclopentenes [C5H5Rh{κ2(C,C)-C(=NMe)CPh=CPhC-(=NR)}(CNR)] (18, 19). Similar compounds 20-23 containing a five-membered RhC4 metallacycle were prepared either from [C5H5Rh(RC≡CR′)(SbiPr3)] (7, 8) or [C5H5Rh-(PhC≡CPh)(CNtBu)] (14) and excess isocyanide. The crystal and molecular structures of 17 and 18 (R = Me) have been determined.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Signatur Availability
    BibTip Others were also interested in ...
  • 9
    ISSN: 0009-2940
    Keywords: Rhodium ; Chelate complexes ; Hydrido complexes ; Bridging ligands ; P Ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mononuclear starting materials [Rh(η4-C8H12)(k2-P,Sb-iPr2PCH2SbR2)]PF6 (la, b) react with CF3CO2H in the presence of H2 to give the dinuclear hydridorhodium(II1) complexes [{RhH(k2-P,Sb-iPr2PCH2SbR2)]PF6 (2a, b) in almost quantitative yield. The X-ray crystal structural analysis of 2b (R = tBu) reveals a distorted octahedral geometry around the two metal centers with the two phosphanyl(stibanyl)methanes in a chelating and the two trifluoracetate ligands in a bridging coordination mode.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Signatur Availability
    BibTip Others were also interested in ...
Close ⊗
This website uses cookies and the analysis tool Matomo. More information can be found here...