Showing papers by "Richard D. Adams published in 2003"
TL;DR: The reaction of Ru(5)(CO)(15)(mu(5)-C), 1, with Pt(PBu(t)(3))(2) at room temperature yielded the mixed-metal cluster complex PtRu(5), 2, in 52% yield, and the reaction of Pd(Pbu(t)3) with compound 1 yielded two new cluster complexes.
Abstract: The reaction of Ru(5)(CO)(15)(mu(5)-C), 1, with Pt(PBu(t)(3))(2) at room temperature yielded the mixed-metal cluster complex PtRu(5)(CO)(15)(PBu(t)(3))(C), 2, in 52% yield. Compound 2 consists of a mixture of two interconverting isomers in solution. One isomer, 2A, can be isolated by crystallization from benzene/octane solvent. The second isomer, 2B, can be isolated by crystallization from diethyl ether. Both were characterized crystallographically. Isomer 2A consists of a square pyramidal cluster of five ruthenium atoms with a phosphine-substituted platinum atom spanning the square base. Isomer 2B consists of a square pyramidal cluster of five ruthenium atoms with a phosphine-substituted platinum atom on an edge on the square base. The two isomers interconvert rapidly on the NMR time scale at 40 degrees C, deltaG(313)++ = 11.4(8) kcal mol(-1), deltaH++ = 8.8(5) kcal mol(-1), deltaS++ = -8.4(9) cal mol(-1) K(-1). The reaction of Pd(PBu(t)(3))(2) with compound 1 yielded two new cluster complexes: PdRu(5)(CO)(15)(PBu(t)(3))(mu(6)-C), 3, in 50% yield and Pd(2)Ru(5)(CO)(15)(PBu(t)(3))(2)(mu(6)-C), 4, in 6% yield. The yield of 4 was increased to 47% when an excess of Pd(PBu(t)(3))(2) was used. In the solid state compound 3 is structurally analogous to 2A, but in solution it also exists as a mixture of interconverting isomers; deltaG(298)++ = 10.6(6) kcal mol(-1), deltaH++ = 9.7(3) kcal mol(-1), and deltaS++ = -3(1) cal mol(-1) K(-1) for 3. Compound 4 contains an octahedral cluster consisting of one palladium atom and five ruthenium atoms with an interstitial carbido ligand in the center of the octahedron, but it also has one additional Pd(PBu(t)(3)) grouping that is capping a triangular face of the ruthenium cluster. The Pd(PBu(t)(3)) groups in 4 also undergo dynamical interchange that is rapid on the NMR time scale at 25 degrees C; deltaG(298)++ = 11(1) kcal mol(-1), deltaH++ = 10.2(4) kcal mol(-1), and deltaS++ = -3(2) cal mol(-1) K(-1) for 4.
54 citations
TL;DR: The reaction of Mn(2)(CO)(7)(mu-S2) with [CpMo(CO)(3](2) (Cp = C(5)H(5)) and Cp*Mo( CO)(3) (2) yielded the new mixed-metal disulfide complexes CpMoMn(CO).
Abstract: The reaction of Mn(2)(CO)(7)(mu-S2) (1) with [CpMo(CO)(3)](2) (Cp = C(5)H(5)) and [Cp*Mo(CO)(3)](2) (Cp* = C(5)(CH(3))(5)) yielded the new mixed-metal disulfide complexes CpMoMn(CO)(5)(mu-S2) (2) and Cp*MoMn(CO)(5)(mu-S2) (3) by a metal-metal exchange reaction. Compounds 2 and 3 both contain a bridging disulfido ligand lying perpendicular to the Mo-Mn bond. The bond distances are Mo-Mn = 2.8421(10) and 2.8914(5) A and S-S = 2.042(2) and 1.9973(10) A for 2 and 3, respectively. A tetranuclear metal side product CpMoMn(3)(CO)(13)(mu3-S)(mu4-S) (4) was also isolated from the reaction of 1 with [CpMo(CO)(3)](2). Compounds 2 and 3 react with CO to yield the dithiocarbonato complexes CpMoMn(CO)(5)[mu-SC(=O)S] (5) and Cp*MoMn(CO)(5)[mu-SC(=O)S] (6) by insertion of CO into the S-S bond. Similarly, tert-butylisocyanide was inserted into the S-S bond of 2 and 3 to yield the complexes CpMoMn(CO)(5)[mu-S(C=NBu(t))S] (7) and Cp*MoMn(CO)(5)[mu-S(C=NBu(t))S] (8), respectively. Ethylene and dimethylacetylene dicarboxylate also inserted into the S-S bond of 2 and 3 at room temperature to yield the ethanedithiolato ligand bridged complexes CpMoMn(CO)(5)(mu-SCH(2)CH(2)S) (9), Cp*MoMn(CO)(5)(mu-SCH(2)CH(2)S) (10), CpMoMn(CO)(5)[mu-SC(CO(2)Me)=C(CO(2)Me)S] (11), and Cp*MoMn(CO)(5)[mu-SC(CO(2)Me)=C(CO(2)Me)S] (12). Allene was found to insert into the S-S bond of 2 by using one of its two double bonds to yield the complex CpMoMn(CO)(5)[mu-SCH(2)C(=CH(2))S] (13). The molecular structures of the new complexes 2-7 and 9-13 were established by single-crystal X-ray diffraction analyses.
41 citations
TL;DR: The molecular structures of the complexes 1-7 were established by single-crystal X-ray diffraction analyses and the reaction yielded the tetranuclear metal complex 2-7.
Abstract: Reaction of CpMoMn(CO)8 with elemental selenium and Me3NO in the absence of light yielded the diselenido complex CpMoMn(CO)5(μ-Se2), 2. Compound 2 contains a bridging diselenido ligand lying perpendicular to the Mo−Mn bond, Mo−Mn = 2.8421(10) A. In the presence of room light, the reaction yielded the tetranuclear metal complex Cp2Mo2Mn2(CO)7(μ3-Se)4, 3 (36% yield), and 2 (7% yield). Compound 2 reacted with ethylene to yield the ethanediselenato complex CpMoMn(CO)5(μ-SeCH2CH2Se), 4, by insertion of ethylene into the Se−Se bond. Compound 2 also reacted with (PPh3)2Pt(PhC2Ph) and CpCo(CO)2 to yield the complexes CpMoMnPt(PPh3)2(CO)5(μ3-Se)2, 5, and Cp2CoMoMn(CO)5(μ3-Se)2, 6, respectively, by insertion of the metal groupings CpCo and Pt(PPh3)2 into the Se−Se bond of 2. The oxo compound Cp2CoMo(O)Mn(CO)5(μ3-Se)2, 7, was obtained from 6 by decarbonylation at molybdenum by using Me3NO. The molecular structures of the complexes 2−7 were established by single-crystal X-ray diffraction analyses.
34 citations
TL;DR: The reaction of Ru5(CO)15(μ5-C), 1, with Ph3GeH at 150 °C has yielded two new germanium-rich pentaruthenium cluster complexes as mentioned in this paper.
Abstract: The reaction of Ru5(CO)15(μ5-C), 1, with Ph3GeH at 150 °C has yielded two new germanium-rich pentaruthenium cluster complexes: Ru5(CO)11(μ-CO)(μ-GePh2)3(μ5-C), 2; Ru5(CO)11(μ-GePh2)4(μ5-C), 3. Both compounds contain square pyramidal Ru5 clusters with GePh2 groups bridging three and four of the edges of the Ru5 square base, respectively. When treated with 1 equiv of Ph3GeH at 150 °C compound 2 is converted to 3. Reaction of 3 with H2 at 150 °C yielded Ru5(CO)10(μ-GePh2)4(μ5-C)(μ-H)2, 4, containing two hydride ligands and one less CO ligand. Reaction of 4 with hydrogen at 150 °C yielded the compound Ru5(CO)10(μ-GePh2)2(μ3-GePh)2(μ3-H)(μ4-CH), 5, by loss of benzene and conversion of two of the bridging GePh2 groups into triply bridging GePh groups. Compound 5 contains one triply bridging hydride ligand and a quadruply bridging methylidyne ligand formed by addition of one hydrogen atom to the carbido carbon atom.
33 citations
TL;DR: In this article, the bridging CO ligand in 1 was replaced by bridging GePh2 group in 4 and a bridging SnPh 2 group in 5, and the lead homologue was obtained from the reaction of 1 with PMe2Ph6.
33 citations
TL;DR: The complexes PtRu (5)(CO)(15)(PMe(2)Ph)(mu(6)-C) (2), PtRu(5)( CO)(14)(P me(3)Ph) (4), Pt Ru(5)(CO)(14) (5), and PtRu-5(CO) (15) (6) were obtained from the reactions of Pt Ru (5) with the appropriate ligand, as determined by NMR spectroscopy.
Abstract: The complexes PtRu(5)(CO)(15)(PMe(2)Ph)(mu(6)-C) (2), PtRu(5)(CO)(14)(PMe(2)Ph)(2)(mu(6)-C) (3), PtRu(5)(CO)(15)(PMe(3))(mu(6)-C) (4), PtRu(5)(CO)(14)(PMe(3))(2)(mu(6)-C) (5), and PtRu(5)(CO)(15)(Me(2)S)(mu(6)-C) (6) were obtained from the reactions of PtRu(5)(CO)(16)(mu(6)-C) (1) with the appropriate ligand. As determined by NMR spectroscopy, all the new complexes exist in solution as a mixture of isomers. Compounds 2, 3, and 6 were characterized crystallographically. In all three compounds, the six metal atoms are arranged in an octahedral geometry, with a carbido carbon atom in the center. The PMe(2)Ph and Me(2)S ligands are coordinated to the Pt atom in 2 and 6, respectively. In 3, the two PMe(2)Ph ligands are coordinated to Ru atoms. In solution, all the new compounds undergo dynamical intramolecular isomerization by shifting the PMe(2)Ph or Me(2)S ligand back and forth between the Pt and Ru atoms. For compound 2, DeltaH++ = 15.1(3) kcal/mol, DeltaS++ = -7.7(9) cal/(mol.K), and DeltaG(298) = 17.4(6) kcal/mol for the transformation of the major isomer to the minor isomer; for compound 4, DeltaH++ = 14.0(1) kcal/mol, DeltaS++ = -10.7(4) cal/(mol.K), and DeltaG(298) = 17.2(2) kcal/mol for the transformation of the major isomer to the minor isomer; for compound 6, DeltaH++ = 18(1) kcal/mol, DeltaS++ = 21(5) cal/(mol.K) and DeltaG(298) = 12(2) kcal/mol. The shifts of the Me(2)S ligand in 6 are significantly more facile than the shifts for the phosphine ligand in compounds 2-5. This is attributed to a more stable ligand-bridged intermediate for the isomerizations of 6 than that for compounds 2-5. The intermediate for the isomerization of 6 involves a bridging Me(2)S ligand that can use two lone pairs of electrons for coordination to the metal atoms, whereas a tertiary phosphine ligand can use only one lone pair of electrons for bridging coordination.
27 citations
TL;DR: PtRu5(CO)16(μ6-C)[Pt(PBut3)] (5); PtRu5'CO'16'm6-c)[PtpBut3]2 (6); Pt Ru5' CO'16'm6c' [Pt'But3]-2 (7); and PtRu 5'CO '16' m6c [Pd'But 3]-2(8) as mentioned in this paper.
22 citations
TL;DR: The disulfido compound CpMoMn(CO)5(μ-S2) (1) reacted with CpCo(CO), and was obtained from 2 by treatment with Me3NO as mentioned in this paper.
22 citations
TL;DR: Methylresorcin[4]arenes in the C2h and C4v symmetrical chair and crown conformers have been synthesized from the typical one-pot acid-catalyzed reaction and structurally characterized.
17 citations
TL;DR: The bisselenido tetramanganese complex, Mn4(CO)15(PPh3)2(μ3-Se)2 (1), was obtained from the reaction of Mn2(CO), 9(NCMe) with SepPh3 as mentioned in this paper.
17 citations
TL;DR: In this paper, the structure of the CpFeMn3(CO)2 group in 4 was determined by single crystal X-ray diffraction analyses, and the core of 3 consists of two [Mn(CO)-3] groups bridged by two disulfido ligands in a μ2−η2 fashion with an additional [mn( CO)4] group that bridges the two disulo ligands.
TL;DR: The reaction of Os3(CO)10(NCMe)2 (1) with an excess of acenaphthylene at room temperature provided the complex O(3CO)9(μ-H)2(μ3-η2-C12H6) (2) when heated to reflux in a cyclohexane solution as discussed by the authors.
TL;DR: In this article, the bis-sulfido mixed metal complexes CpMoMn(CO)5Pt(PPh3)2Pt (PhC2Ph)2(μ-S2), 2a, 2b, 2c, Cp=C5H5 and Cp*MoMmn(C5Me5) with Pd(PBu� tcffff � � �� 3)2.
Abstract: The reaction of the complexes CpMoMn(CO)5(μ-S2), 2a, Cp=C5H5 and Cp*MoMn(CO)5(μ-S2), 2b, Cp*=C5Me5with (PPh3)2Pt(PhC2Ph) yielded the new bis-sulfido mixed metal complexes CpMoMn(CO)5Pt(PPh3)2(μ
3-S)2, 3a and Cp*MoMn(CO)5Pt(PPh3)2(μ
3-S)2, 3b by insertion of a platinum metal grouping into the S–S bond. A mono-phosphine complex, Cp*MoMn(CO)6Pt(PPh3)(μ
3-S)2, 4b was also isolated from the reaction of 2b with (PPh3)2Pt(PhC2Ph). Compounds 3b and 4b were both characterized crystallographically. Both complexes consist of open MoMnPt clusters with a Mo–Mn single bond, Mo–Mn=2.7570(16) A for 3b and Mo–Mn=2.7837(13) A for 4b, and two triply bridging sulfido ligands. The trimetallic complexes CpMo(O)MnPd(PBu
t
3)(CO)5(μ
3-S), 5a and Cp*Mo(O)MnPd(PBu
t
3)(CO)5(μ
3-S), 5b containing an oxo ligand bonded to molybdenum were obtained from the reaction of 2a–b with Pd(PBu
t
3)2. The molecular structure of the 5a was also established crystallographically.