... TP, unpublished results for (Cp49zMg (6) Burkey, DJ; Alexander, E. IC; Hanusa, TP Organometal... more ... TP, unpublished results for (Cp49zMg (6) Burkey, DJ; Alexander, E. IC; Hanusa, TP Organometallics 1994,13,2773-2786. Sn. Analytical and spectroscopic (lH, 13C NMR, IR) data for the two metallocenes confirm the proposed formula-tion~.~ An X-ray crystallographic study ...
Acta Crystallographica Section C-crystal Structure Communications, Oct 15, 1996
PtC12(C4H7N30)2].2H20 2260 reflections 104 parameters H atoms riding, except for those of the wat... more PtC12(C4H7N30)2].2H20 2260 reflections 104 parameters H atoms riding, except for those of the water molecule w = l/[cr2(Fo 2) + (0.0195P) 2] where P = (F 2 + 2F2)/3 Extinction correction: none Atomic scattering factors from International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) Lists of structure factors, anisotropic displacement parameters, Hatom coordinates and complete geometry have been deposited with the IUCr (Reference: FGII17). Copies may be obtained through The Managing Editor,
Abstract 1,2,4-tricyclohexylcyclopentadiene can be formed from the phase-transfer catalysed addit... more Abstract 1,2,4-tricyclohexylcyclopentadiene can be formed from the phase-transfer catalysed addition of cyclohexyl bromide to cyclopentadiene. Reaction of two equivalents of its lithium salt with FeCl 2 in THF produces the corresponding substituted ferrocene. Crystals of orange [1,2,4-(C 6 H 11 ) 3 C 5 H 2 ] 2 Fe grown from toluene are monoclinic, space group C 2/ c , with a = 16.386 (4) A, b = 12.142 (3) A, c = 21.003 (3) A, β = 107.38 (1), and D calcd = 1. 131 g cm −3 for Z = 4. Least- squares refinement based on 1291 observed reflections led to a final R value of 0.049. The molecule possesses a classic sandwich geometry with staggered rings and a crystallographically imposed two-fold rotation axis passing through the metal center. Despite the presence of six cyclohexyl rings, the cyclopentadienyl ligands can orient themselves around the iron to avoid unfavorable inter- ring steric interactions. As a result, the average Fe-C ring distance of 2.06 (1) A in hexa(cyclohexyl)ferrocene is not significantly longer than the corresponding distance in ferrocene itself.
An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
Solution-based reactions are a staple of synthetic chemistry—but what happens mechanochemically, ... more Solution-based reactions are a staple of synthetic chemistry—but what happens mechanochemically, when there is no solvent?
... William J. Evans," Timothy P. Hanusa, and James H. Meadows ... to that of Churchill ... more ... William J. Evans," Timothy P. Hanusa, and James H. Meadows ... to that of Churchill was employed.38 Calculations were carried out with the SHELX system of computer pr0grams.3~ Neutral atom scattering factors for Y, N, and C were taken from Cromer and Waber,@ and the ...
... William J. Evans, ' Raul Dominguez, and Timothy P. Hanusa ... (2) Marks, TJ; Emst, R... more ... William J. Evans, ' Raul Dominguez, and Timothy P. Hanusa ... (2) Marks, TJ; Emst, RD In Comprehensive Organometallic Chemktry; WilLineon, G., Stone, FGA, Abel, EW, Eds.; Pergamon: Oxford, 1982; Chapter 21 and references therein. (3) Evans, W. J. Adu. Organomet. Chem. ...
In the more than 50 years since the first manganese compound with MnC bonds was crystallographica... more In the more than 50 years since the first manganese compound with MnC bonds was crystallographically characterized (Mn2(CO)10, in 1957), the number of structurally authenticated organomanganese compounds has grown to several thousands. The richness of structural features in organomanganese compounds now rivals that of any other first row transition metal. The range of structural features and bond types is large, and encompasses MnC, MnC, and MnC bonds, as well as complexes with MnMn, MnMn, and MnMn linkages. Crystallographically characterized examples are known with oxidation states from Mn0 to MnV, and the accessibility of two spin states of comparable energy in complexes of MnII adds an additional variable to the fundamental structural types. The present review of structural organomanganese chemistry focuses largely on crystallographically characterized complexes, whose geometries are the most reliably established. Representative examples of major compound classes are considered, and statistical analysis of typical bond length ranges is provided for various Mn/C and Mn/Mn interactions. Bond lengths in organomanganese compounds are highly context-sensitive, and even when only a specific bond order is under consideration, the spread of distances makes comparisons difficult unless closely related molecules are examined. Keywords: cyclopentadienyl complexes; cymantrene; manganese; manganocene; organometallic chemistry; paramagnetic compounds; solid-state structures; spin states; steric bulk; X-ray crystallography
for 2105 unique observed data. The cyclopentadienyl ring is bonded in a pentahapto manner to the ... more for 2105 unique observed data. The cyclopentadienyl ring is bonded in a pentahapto manner to the Cu, with Cu-C = 2.214 (6) A (ave.). The ring-centroid-CuP grouping forms a nearly linear array (173.1 o) for which Cu-centroid = 1.865 (9) A and CuP = 2.131 A. Around P, the geometry is roughly tetrahedral. Introduction. The pentahapto cyclopentadienyl ligand, although ubiquitous in most areas of organometallic chemistry, is rare among complexes of the Cu triad. For Cu itself, few structural studies are available which present information on the metal-cyclopentadienyl interaction. Only two early studies provide details pertaining to the Cu-CsH 5 unit: (q-CsHs)CuPPh 3 (Cotton & Takats, 1970) and (r/-CsHs)CuPEt 3 (Delbaere, McBride & Ferguson, 1970). Recently, a communication on the structures of two metal clusters, (r/-CsM%)3RhECu(CO) 2 and (r/-CsMes)(r/-CsHs) ~-CC6H4Me-4)PtWCu(CO)2(PMe3) 2, containing the (r/-CsMes)Cu fragment has appeared (Carriedo, Howard & Stone, 1983), but the focal point of the investigation was not the detailed structure of the cyclopentadienylcopper unit. This X-ray diffraction study of the title compound provides structural information on a substituted cyclopentadienyl-copper system and permits comparison with the known (r/-CsHs)CuPR 3 structures. Experimental. Complex prepared from reaction of Na(CH3CsH4) with PhaPCuC1 in THF (Cotton & Marks, 1970). Colorless crystals grown from hexane solution at room temperature. Crystal 0.15 × 0.35 × 0.42 mm sealed in glass capillary under N 2. Syntex P2~ diffractometer, graphite-monochromated Mo Ka. Lattice parameters from setting angles of 15 reflections with 13 °<20<23 °. Systematic absences hkl, h+k+ 14= 2n; hOl, h 4= 2n. /-centered setting allowed use of smaller fl angle than that required by an A-centered cell * To whom correspondence should be addressed.
Journal of the American Chemical Society, Aug 1, 1984
Improved syntheses of several trimetallic tetrahydride complexes (tri(diphenyl lanthanon hydride)... more Improved syntheses of several trimetallic tetrahydride complexes (tri(diphenyl lanthanon hydride)-lithium tetrahydrofuran) were studied using lithium hydride, methyl hydride, and tetra-butyl lithium reacted with diphenyl yttrium hydride tetrahydrofuran dimer. The reaction with tetra-butyl lithium yields the trimer as above while the reaction with diphenyl yttrium deuteride tetrahydrofuran with tert-butyl lithium forms a perdeuterio trimer indicating that the tert-butyl group does not provide a negative hydrogen ion for the trimer. Proton NMR spectra of some of the compounds are presented with H-H, Y-H, and Y-Y couplng constants derived from computer simulation of the spectra.
C,Me,@m(THF), can be desolvated at 75 ' C under high vacuum to form the green complex (C&e&$m, wh... more C,Me,@m(THF), can be desolvated at 75 ' C under high vacuum to form the green complex (C&e&$m, which sublmes at 85 O C and 1Oa torr. Single crystals grown by sublimation crystallize in the space group R , / n with a = 9.815 (3) A, b = 13.436 (9) A, c = 14.163 (8) A, 6 = 94.98 (4)', v = 1861 (2) A3, and Deal,.. = 1.500 g cm-3 for 2 = 4. Least-squares refinement on the basis of 2636 unique observed reflections (I > 3 4) converged to a final R = 0.035. The molecule exhibits a bent structure with a (ring centroid)-Sm-(ring centroid) angle of 140.1O and an average Sm-cyclopentadienyl carbon distance of 2.79 (1) A. Repeated sublimation of (C5Me5),Eu(THF) at 70 "C under high vacuum yields the deep red unsolvated complex (C6Me6)2Eu. X-ray quality crystals grown by resublimation form in the s ace group P2,/n with a = 9.838 (4) A, b = 13.443 (4) A, c = 14.174 (3) A, 6 = 95.03 (2)', v = 1867 (2) &, and.D,dcd = 1.503 g cmS for 2 = 4. Full-matrix least-squares refinement on the basis of 2543 unique reflections (I 1 3a (I)) converged to R = 0.055. (CSMe6),Eu is isomorphous and isostructural with (C6Me5),Srn. It possesses a bent metallmne structure with a (ring centroid)-Eu-(ring centroid) angle of 140.3' and an average Eu-C(q5) distance of 2.79 (1) A.
ChemInform Abstract Die Hydrogenolyse der durch Methylierung mit Methyl-Li aus den ChIor-Analogen... more ChemInform Abstract Die Hydrogenolyse der durch Methylierung mit Methyl-Li aus den ChIor-Analogen dargesteilten Y(III)-Dimeren (I) liefert die Hydrid-IJimeren (II). Diese setzen sich mit Nitrilen durch 1,2-Addition der Y-a-H-Bindung zu den dimeren Alkylidenamido-Komplexen (III) um. MoleküI-und Kristallstrukturdaten für (IIIb) (R': H; RG PI, Z=2) werden bestimmt. Die Hydrid-[)imeren (II) reagieren mit Ethylen und Propylen zu den monomeren Alkyl-Komplexen (IV), mit Allen zu den if-AIIyI-Derivaten (V), mit dem terminalen Alkin tert.-Butylacetylen zu den Alkinid-[)imeren (VI), mit inneren Alkinen zu den monomeren A kenyI-Derivaten (VII), mit Pyridin in unpolaren Lösungsmitteln zu Pyridin-Analogen von (II), aber mit Pyridin in polaren Lösungsmitteln zu demüber sein I,2-Isomeres entstehenden 1,4-Isomeren des Komplexes (IX). (IIb) und (VIIb) sind Katalysatorenpfür die Hg-Aktivierung in AIkin-Hydrierungsreaktionen. (Neben den aufgeführten Ausb. nur für (VIII) Ausb. in mg.
Skip to Main Content. Wiley Online Library will be unavailable 17 Dec from 10-13 GMT for IT maint... more Skip to Main Content. Wiley Online Library will be unavailable 17 Dec from 10-13 GMT for IT maintenance. ...
The reaction of the phosphido-bridged metal carbonyl [FeRh(CO)ö(At-PBu2)] (1) with dppm [dppm = b... more The reaction of the phosphido-bridged metal carbonyl [FeRh(CO)ö(At-PBu2)] (1) with dppm [dppm = bis(diphenylphosphino)methane] leads to the heterobimetallic complex [FeRh(/z-CO)(CO)3()U-PBu2)(/i-dppm)] (2) in good yields. The molecular structure of 2 was determined at room temperature [triclinic, space group Pi, a = 9.509(6), b = 13.637(5), c = 14.926(8) A, q = 81.38(4), ß = 82.75(4), 7 = 71.25(4)°]. The compound acts as a homogeneous catalyst precursor in the hydroformylation reaction of ethylene, but it decomposes during this process.
The complex (I) reacts with 2,3,5‐6‐tetramethylphenoI (II) to yield the title compound (III), whi... more The complex (I) reacts with 2,3,5‐6‐tetramethylphenoI (II) to yield the title compound (III), which crystallizes in the space group P21/c with Z=4.
... TP, unpublished results for (Cp49zMg (6) Burkey, DJ; Alexander, E. IC; Hanusa, TP Organometal... more ... TP, unpublished results for (Cp49zMg (6) Burkey, DJ; Alexander, E. IC; Hanusa, TP Organometallics 1994,13,2773-2786. Sn. Analytical and spectroscopic (lH, 13C NMR, IR) data for the two metallocenes confirm the proposed formula-tion~.~ An X-ray crystallographic study ...
Acta Crystallographica Section C-crystal Structure Communications, Oct 15, 1996
PtC12(C4H7N30)2].2H20 2260 reflections 104 parameters H atoms riding, except for those of the wat... more PtC12(C4H7N30)2].2H20 2260 reflections 104 parameters H atoms riding, except for those of the water molecule w = l/[cr2(Fo 2) + (0.0195P) 2] where P = (F 2 + 2F2)/3 Extinction correction: none Atomic scattering factors from International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) Lists of structure factors, anisotropic displacement parameters, Hatom coordinates and complete geometry have been deposited with the IUCr (Reference: FGII17). Copies may be obtained through The Managing Editor,
Abstract 1,2,4-tricyclohexylcyclopentadiene can be formed from the phase-transfer catalysed addit... more Abstract 1,2,4-tricyclohexylcyclopentadiene can be formed from the phase-transfer catalysed addition of cyclohexyl bromide to cyclopentadiene. Reaction of two equivalents of its lithium salt with FeCl 2 in THF produces the corresponding substituted ferrocene. Crystals of orange [1,2,4-(C 6 H 11 ) 3 C 5 H 2 ] 2 Fe grown from toluene are monoclinic, space group C 2/ c , with a = 16.386 (4) A, b = 12.142 (3) A, c = 21.003 (3) A, β = 107.38 (1), and D calcd = 1. 131 g cm −3 for Z = 4. Least- squares refinement based on 1291 observed reflections led to a final R value of 0.049. The molecule possesses a classic sandwich geometry with staggered rings and a crystallographically imposed two-fold rotation axis passing through the metal center. Despite the presence of six cyclohexyl rings, the cyclopentadienyl ligands can orient themselves around the iron to avoid unfavorable inter- ring steric interactions. As a result, the average Fe-C ring distance of 2.06 (1) A in hexa(cyclohexyl)ferrocene is not significantly longer than the corresponding distance in ferrocene itself.
An entry from the Cambridge Structural Database, the world's repository for small molecule cr... more An entry from the Cambridge Structural Database, the world's repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
Solution-based reactions are a staple of synthetic chemistry—but what happens mechanochemically, ... more Solution-based reactions are a staple of synthetic chemistry—but what happens mechanochemically, when there is no solvent?
... William J. Evans,&quot; Timothy P. Hanusa, and James H. Meadows ... to that of Churchill ... more ... William J. Evans,&quot; Timothy P. Hanusa, and James H. Meadows ... to that of Churchill was employed.38 Calculations were carried out with the SHELX system of computer pr0grams.3~ Neutral atom scattering factors for Y, N, and C were taken from Cromer and Waber,@ and the ...
... William J. Evans, &#x27; Raul Dominguez, and Timothy P. Hanusa ... (2) Marks, TJ; Emst, R... more ... William J. Evans, &#x27; Raul Dominguez, and Timothy P. Hanusa ... (2) Marks, TJ; Emst, RD In Comprehensive Organometallic Chemktry; WilLineon, G., Stone, FGA, Abel, EW, Eds.; Pergamon: Oxford, 1982; Chapter 21 and references therein. (3) Evans, W. J. Adu. Organomet. Chem. ...
In the more than 50 years since the first manganese compound with MnC bonds was crystallographica... more In the more than 50 years since the first manganese compound with MnC bonds was crystallographically characterized (Mn2(CO)10, in 1957), the number of structurally authenticated organomanganese compounds has grown to several thousands. The richness of structural features in organomanganese compounds now rivals that of any other first row transition metal. The range of structural features and bond types is large, and encompasses MnC, MnC, and MnC bonds, as well as complexes with MnMn, MnMn, and MnMn linkages. Crystallographically characterized examples are known with oxidation states from Mn0 to MnV, and the accessibility of two spin states of comparable energy in complexes of MnII adds an additional variable to the fundamental structural types. The present review of structural organomanganese chemistry focuses largely on crystallographically characterized complexes, whose geometries are the most reliably established. Representative examples of major compound classes are considered, and statistical analysis of typical bond length ranges is provided for various Mn/C and Mn/Mn interactions. Bond lengths in organomanganese compounds are highly context-sensitive, and even when only a specific bond order is under consideration, the spread of distances makes comparisons difficult unless closely related molecules are examined. Keywords: cyclopentadienyl complexes; cymantrene; manganese; manganocene; organometallic chemistry; paramagnetic compounds; solid-state structures; spin states; steric bulk; X-ray crystallography
for 2105 unique observed data. The cyclopentadienyl ring is bonded in a pentahapto manner to the ... more for 2105 unique observed data. The cyclopentadienyl ring is bonded in a pentahapto manner to the Cu, with Cu-C = 2.214 (6) A (ave.). The ring-centroid-CuP grouping forms a nearly linear array (173.1 o) for which Cu-centroid = 1.865 (9) A and CuP = 2.131 A. Around P, the geometry is roughly tetrahedral. Introduction. The pentahapto cyclopentadienyl ligand, although ubiquitous in most areas of organometallic chemistry, is rare among complexes of the Cu triad. For Cu itself, few structural studies are available which present information on the metal-cyclopentadienyl interaction. Only two early studies provide details pertaining to the Cu-CsH 5 unit: (q-CsHs)CuPPh 3 (Cotton & Takats, 1970) and (r/-CsHs)CuPEt 3 (Delbaere, McBride & Ferguson, 1970). Recently, a communication on the structures of two metal clusters, (r/-CsM%)3RhECu(CO) 2 and (r/-CsMes)(r/-CsHs) ~-CC6H4Me-4)PtWCu(CO)2(PMe3) 2, containing the (r/-CsMes)Cu fragment has appeared (Carriedo, Howard & Stone, 1983), but the focal point of the investigation was not the detailed structure of the cyclopentadienylcopper unit. This X-ray diffraction study of the title compound provides structural information on a substituted cyclopentadienyl-copper system and permits comparison with the known (r/-CsHs)CuPR 3 structures. Experimental. Complex prepared from reaction of Na(CH3CsH4) with PhaPCuC1 in THF (Cotton & Marks, 1970). Colorless crystals grown from hexane solution at room temperature. Crystal 0.15 × 0.35 × 0.42 mm sealed in glass capillary under N 2. Syntex P2~ diffractometer, graphite-monochromated Mo Ka. Lattice parameters from setting angles of 15 reflections with 13 °<20<23 °. Systematic absences hkl, h+k+ 14= 2n; hOl, h 4= 2n. /-centered setting allowed use of smaller fl angle than that required by an A-centered cell * To whom correspondence should be addressed.
Journal of the American Chemical Society, Aug 1, 1984
Improved syntheses of several trimetallic tetrahydride complexes (tri(diphenyl lanthanon hydride)... more Improved syntheses of several trimetallic tetrahydride complexes (tri(diphenyl lanthanon hydride)-lithium tetrahydrofuran) were studied using lithium hydride, methyl hydride, and tetra-butyl lithium reacted with diphenyl yttrium hydride tetrahydrofuran dimer. The reaction with tetra-butyl lithium yields the trimer as above while the reaction with diphenyl yttrium deuteride tetrahydrofuran with tert-butyl lithium forms a perdeuterio trimer indicating that the tert-butyl group does not provide a negative hydrogen ion for the trimer. Proton NMR spectra of some of the compounds are presented with H-H, Y-H, and Y-Y couplng constants derived from computer simulation of the spectra.
C,Me,@m(THF), can be desolvated at 75 ' C under high vacuum to form the green complex (C&e&$m, wh... more C,Me,@m(THF), can be desolvated at 75 ' C under high vacuum to form the green complex (C&e&$m, which sublmes at 85 O C and 1Oa torr. Single crystals grown by sublimation crystallize in the space group R , / n with a = 9.815 (3) A, b = 13.436 (9) A, c = 14.163 (8) A, 6 = 94.98 (4)', v = 1861 (2) A3, and Deal,.. = 1.500 g cm-3 for 2 = 4. Least-squares refinement on the basis of 2636 unique observed reflections (I > 3 4) converged to a final R = 0.035. The molecule exhibits a bent structure with a (ring centroid)-Sm-(ring centroid) angle of 140.1O and an average Sm-cyclopentadienyl carbon distance of 2.79 (1) A. Repeated sublimation of (C5Me5),Eu(THF) at 70 "C under high vacuum yields the deep red unsolvated complex (C6Me6)2Eu. X-ray quality crystals grown by resublimation form in the s ace group P2,/n with a = 9.838 (4) A, b = 13.443 (4) A, c = 14.174 (3) A, 6 = 95.03 (2)', v = 1867 (2) &, and.D,dcd = 1.503 g cmS for 2 = 4. Full-matrix least-squares refinement on the basis of 2543 unique reflections (I 1 3a (I)) converged to R = 0.055. (CSMe6),Eu is isomorphous and isostructural with (C6Me5),Srn. It possesses a bent metallmne structure with a (ring centroid)-Eu-(ring centroid) angle of 140.3' and an average Eu-C(q5) distance of 2.79 (1) A.
ChemInform Abstract Die Hydrogenolyse der durch Methylierung mit Methyl-Li aus den ChIor-Analogen... more ChemInform Abstract Die Hydrogenolyse der durch Methylierung mit Methyl-Li aus den ChIor-Analogen dargesteilten Y(III)-Dimeren (I) liefert die Hydrid-IJimeren (II). Diese setzen sich mit Nitrilen durch 1,2-Addition der Y-a-H-Bindung zu den dimeren Alkylidenamido-Komplexen (III) um. MoleküI-und Kristallstrukturdaten für (IIIb) (R': H; RG PI, Z=2) werden bestimmt. Die Hydrid-[)imeren (II) reagieren mit Ethylen und Propylen zu den monomeren Alkyl-Komplexen (IV), mit Allen zu den if-AIIyI-Derivaten (V), mit dem terminalen Alkin tert.-Butylacetylen zu den Alkinid-[)imeren (VI), mit inneren Alkinen zu den monomeren A kenyI-Derivaten (VII), mit Pyridin in unpolaren Lösungsmitteln zu Pyridin-Analogen von (II), aber mit Pyridin in polaren Lösungsmitteln zu demüber sein I,2-Isomeres entstehenden 1,4-Isomeren des Komplexes (IX). (IIb) und (VIIb) sind Katalysatorenpfür die Hg-Aktivierung in AIkin-Hydrierungsreaktionen. (Neben den aufgeführten Ausb. nur für (VIII) Ausb. in mg.
Skip to Main Content. Wiley Online Library will be unavailable 17 Dec from 10-13 GMT for IT maint... more Skip to Main Content. Wiley Online Library will be unavailable 17 Dec from 10-13 GMT for IT maintenance. ...
The reaction of the phosphido-bridged metal carbonyl [FeRh(CO)ö(At-PBu2)] (1) with dppm [dppm = b... more The reaction of the phosphido-bridged metal carbonyl [FeRh(CO)ö(At-PBu2)] (1) with dppm [dppm = bis(diphenylphosphino)methane] leads to the heterobimetallic complex [FeRh(/z-CO)(CO)3()U-PBu2)(/i-dppm)] (2) in good yields. The molecular structure of 2 was determined at room temperature [triclinic, space group Pi, a = 9.509(6), b = 13.637(5), c = 14.926(8) A, q = 81.38(4), ß = 82.75(4), 7 = 71.25(4)°]. The compound acts as a homogeneous catalyst precursor in the hydroformylation reaction of ethylene, but it decomposes during this process.
The complex (I) reacts with 2,3,5‐6‐tetramethylphenoI (II) to yield the title compound (III), whi... more The complex (I) reacts with 2,3,5‐6‐tetramethylphenoI (II) to yield the title compound (III), which crystallizes in the space group P21/c with Z=4.
Uploads
Papers by Timothy Hanusa