Darstellung, 11B-NMR- und Schwingungsspektren mehrfach alkylierter closo-Hexaborate und Kristallstruktur von cis- und trans-[P(C6H5)4][B6H5(CH3)2] sowie mer-[P(C6H5)4][B6H4(CH3)3] / Preparation, 11B NMR and Vibrational Spectra of Multialkylated Hexaborates and Crystal Structures of cis- and trans-[P(C6H5)4][B6H5(CH3)2] and mer-[P(C6H5)4][B6H4(CH3)3]

1995 ◽  
Vol 50 (5) ◽  
pp. 772-780 ◽  
Author(s):  
J. Baurmeister ◽  
A. Franken ◽  
W. Preetz
Keyword(s):  
Crystal Structures ◽  
Methyl Iodide ◽  
Exchange Chromatography ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Space Group ◽  
Yellow Orange ◽  
11B Nmr ◽  
Cis And Trans ◽  
Ir And Raman

Abstract By treatment of protonated monoalkyl-closo-hexaborates [B6H6R]-. R = CH3, C2H5, n-C3H7, i-C3H7 in aqueous alkaline solution with [As(C6H5)4]Cl the yellow orange deprotonated tetraphenylarsonium salts are precipitated, which react with methyl iodide or ethyl iodide to give dialkylated and protonated B6-compounds. The cisltrans isomers formed in a 1:1 ratio have been separated by ion exchange chromatography on diethylam inoethyl cellulose. Repeated deprotonation and reaction with methyl iodide affords mer-[B6H4 (CH3)3]-. The crystal structures of cis-[P(C6H5)4][B6H5(CH3)2] (I), trans-[P(C6H5)4][B6H5(CH3)2] (II) and mer-[P(C6H5)4][B6H4(CH3)3](III) have been determined by single crystal X-ray diffraction analyses; I and II are monoclinic, space group P2/n, I with a = 11.8690(5), b = 7.2575(7), c = 15.8689(3) Å , β = 111.454(17)°; II with a = 13.2853(7), b = 7.4608(8), c = 13.3549(11), β = 93.5(11); III is tetragonal, space group P4/n with a = 13.363(2), c = 7.5051(13). The three methyl substituents are statistically distributed over four equatorial positions of the B6 cage. The 11B NMR spectra of the di- and trialkylated com pounds exhibit shifts of ipso-B atoms to lower, of antipodal-B atoms to higher field compared with [B6H7]-. The IR and Raman spectra of the di- and trimethyl derivatives are similar to those of monom ethylhexaborate.

Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von cis- und trans-[ReCl4 (NCSe)(SeCN)]2- / Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of cis- and trans-[ReCl4 (NCSe)(SeCN)]2-

1999 ◽  
Vol 54 (3) ◽  
pp. 357-362 ◽  
Author(s):  
S. Strueß ◽  
W. Preetz
Keyword(s):  
Low Temperature ◽  
Crystal Structures ◽  
Normal Coordinate Analysis ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Normal Coordinate ◽  
Space Group ◽  
X Ray ◽  
Cis And Trans ◽  
Ir And Raman

The crystal structures of cis-(n-Bu4N)2[ReCl4(NCSe)(SeCN)] (monoclinic, space group P21/n a = 10.794(3), b = 11.687(3), c = 35.716(4) Å, β = 96.97(1)°, Z = 4) and trans- (CH2Py2)[ReCl4(NCSe)(SeCN)] (monoclinic, space group P21/c, a = 8.348(2), b = 7.518(1), c - 31.295(7) Å, ß = 97.12(2)°, Z = 4) have been determined by single crystal X-ray diffraction analysis. Based on the molecular parameters of the X-ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu4N) salts have been assigned by normal coordinate analysis. The valence force constants are fd(ReN) = 1.68 and fd(ReSe) =1.15 mdyn/Å.

Darstellung, 11 B-NMR-, Schwingungsspektren und Kristallstruktur von Bis(tetraphenylphosphonium)-2-[2-(2-pyridyl-amino)-pyrid-5-yl]-closo-decaborat, [P(C6H5)4]2[2-{2-(2-(C5H4N)-NH)-(C5H3N)-5}B10H9] / Preparation, 11B NMR, Vibrational Sprectra and Crystal Structure of Bis(tetraphenylphosphonium) 2-[2-(2-Pyridyl-amino)-pyrid-5-yl]-closo-decaborate, [P(C6H5)4]2 [2-{2-(2-(C5H4N)-NH)-(C5H3N)-5}B10H9]

1996 ◽  
Vol 51 (11) ◽  
pp. 1559-1562 ◽  
Author(s):  
C. Nachtigal ◽  
W. Preetz
Keyword(s):  
Crystal Structure ◽  
Deae Cellulose ◽  
Exchange Chromatography ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Nmr Spectrum ◽  
Closo Decaborate Anion ◽  
11B Nmr ◽  
Stretching Vibrations ◽  
Ir And Raman

By reaction of [N(C4H9)4]2[B10H10] with 2, 2′-(C5H5N)2NH at 160 °C the 2-[2-(2-pyridylamino)- pyrid-5-yl]-closo-decaborate anion [2-{2-(2-(C5H4N)-NH)-(C5H3N)-5 }B10H9]2− is obtained which can be separated from excess [B10H10]2− by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose. The crystal structure of [P(C6H5)4]2[2-{2-(2-(C5H4N)- NH)-(C5H3N)-5 }B10H9] has been determinated by single crystal X-ray diffraction analysis: monoclinic, space group P21/n with a = 11.435(3), b = 22.923(2), c = 20.094(4) Å, β = 95,27(2)°, Z = 4. By influence of the substituent the B10 cage is strongly distorted with B-B distances ranging from 1.522 to 2.188 Å. The 11B NMR spectrum reveals the feature (2:1:7) of a B10 cage with the substituent in the 2 position with a downfield shift of the ipso B atom at −20.2 ppm. The IR and Raman spectra exhibit characteristic BH stretching vibrations between 2416 and 2499 cm −1 and the (C-C) and (C-N) stretching vibrations in the range of 1306 to 1584 cm −1 .

Darstellung, Schwingungsspektren und Normalkoordinatenanalyse von bindungsisomeren Halogenoselenocyanatorhenaten(IV) sowie Kristallstrukturen von mer-(Ph4P)2[ReCl3(NCSe)2cis (SeCN)] und mer-(n-Bu4N)2[ReCl3I(NCSe)2cis] / Synthesis, Vibrational Spectra and Normal Coordinate Analysis of Linkage Isomeric Halogenoselenocyanatorhenates(IV) and Crystal Structures of mer-(Ph4P)2[ReCl3(NCSe)2cis (SeCN)] and mer-(n-Bu4N)2[ReCl3I(NCSe)2cis]

1999 ◽  
Vol 54 (10) ◽  
pp. 1222-1228 ◽  
Author(s):  
S. Strueß ◽  
W. Preetz
Keyword(s):  
Crystal Structures ◽  
Exchange Chromatography ◽  
Normal Coordinate Analysis ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Normal Coordinate ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Diethylaminoethyl Cellulose

By treatment of fac-[ReCl3I3]2- with (SeCN)2 indichloromethane fac-[ReCl3(NCSe)3]2- (1), mer-[ReCl3(NCSe)2cis (SeCN)]2- (2) and mer-[ReCl3I(NCSe)2cis]2- (3) are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structures of mer-(Ph-P)2[ReCl3(NCSe)2cis(SeCN)] (triclinic, space group Pl̅, a = 16.099(1), b = 16.729(3), c =21.026(2) Å, α = 70.194(10), ß = 73.958(10), γ = 83.929(10)°, Z = 4) and mer-(n-Bu4N)2[ReCl3|(NCSe)2cis] (monoclinic, space group P21/c, a = 11.838(1), b = 12.796(2), c = 30.767(2) Å, ß = 97.419(6)°, Z = 4) have been determined by single crystal X-ray diffraction analysis. Based on the molecular parameters of the X-ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu4N) salts have been assigned by normal coordinate analysis. The valence force constants are fd(ReN) = 1.79 (1), 1.71 (2), 1.71 (3) and fd(ReSe) = 1.15 (2) mdyn/Å.

Kristallstrukturen, Schwingungsspektren und Normalkoordinaten- analysen von trans-[OsO2(ox)2]2– und trans-[OsO2(mal)2]2–/ Crystal Structures, Vibrational Spectra and Normal Coordinate Analyses of trans-[OsO2(ox)2]2– and trans -[OsO2(mal)2]2–

1998 ◽  
Vol 53 (8) ◽  
pp. 823-828 ◽  
Author(s):  
A. Strueß ◽  
W. Preetz
Keyword(s):  
Crystal Structures ◽  
Vibrational Spectra ◽  
Room Temperature ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Normal Coordinate ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Ir And Raman

Abstract The crystal structures of trans-(Ph4P)2[OsO2(ox)2] (monoclinic, space group P21/n, a = 12.281(2), b = 14.5440(13), c = 13.9810(12) Å, β = 100.000(8)°, Z = 2) and trans- (n-Bu4N)2[OsO2(mal)2] (triclinic, space group P1̄, a = 10.365(4),b = 10.707(3), c - 11.473(5) A, a = 73.00(2), β = 64.44(3), 7 = 82.55(3)°, Z = 1) have been determined by single crystal X-ray diffraction analysis. The IR and Raman spectra of these complexes were measured at room temperature. Based on the molecular parameters of the X-ray determinations normal coordinate analyses have been performed and the vibrations assigned. The valence force constants of [OsO2(ox)2]2- are fd(Os=O) = 6.7, fd(Os-O) = 2.9, fd(C-O) = 5.05, fd(C=O) = 11.2 and fd(C-C) = 4.7 mdyn/Å and of [OsO2(mal)2]2- fd(Os=O) = 6.7, fd(Os-O) = 2.9, fd(C-O) = 4.86, fd(C=O) =11.1 and fd(C-C) = 4.07 mdyn/Å.

Darstellung, 11B-NMR- und Schwingungsspektren von cis-Monocyanomononitrotetrahydro-closo-hexaborat(2-) , as-[B6H4(CN)(NO2)]2- und cis-μ-Nitroso-bis(monocyanotetrahydro-closo-hexaborat)(3-), cis-[(CN)B6H4(NO)B6H4(CN)]3– sowie Kristallstruktur von [As(C6H5)4]2-cis-[B6H4(CN)(NO2)] / Preparation, n=11B-NMR and Vibrational Spectra of cis-Monocyanomononitrotetrahydro-closo-hexaborate(2-) , cis-[B6H4(CN)(NO2)]2-,cis -μ-Nitroso-bis(monocyanotetrahydro-hexaborate)(3-), cis-[(CN)B6H4(NO)B6H4(CN)]3– and the Crystal Structure of [As(C6H5)4]2-cis-[B6H4(CN)(NO2)]

1995 ◽  
Vol 50 (9) ◽  
pp. 1362-1368 ◽  
Author(s):  
A. Franken ◽  
W. Preetz
Keyword(s):  
Crystal Structure ◽  
Ion Exchange Chromatography ◽  
Exchange Chromatography ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Dichloromethane Solution ◽  
X Ray ◽  
Diethylaminoethyl Cellulose ◽  
11B Nmr ◽  
Ir And Raman

AbstractBy electrochemical oxidation of [B6H5(CN)]2- in the presence of nitrite ions and of the base DBU in dichloromethane solution cis-[B6H4(CN)(NO2)]2- and cis- [(CN)B6H4(NO)B6H4(CN)]3- are formed and can be isolated by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structure of the tetraphenylarsonium salt has been determined by single crystal X-ray diffraction analysis. [As(C6H5)4]2-cis-[B6H4(CN)(NO2)] is monoclinic, space group P21/a with a = 20.343(5), b = 10.896(2), c = 21.572(5) A and β = 107.30(2)°. The 11B NMR spectra are consistent with disubstituted octahedral B6 cages with local C2v symmetry. The IR and Raman spectra exhibit characteristic NO2, NO, CN, BH, and B6 vibrations.

Darstellung, 11B-, 13C-, 1H-NMR- und Schwingungsspektren von 1.2-Trimethylenpentahydro-closo-Hexaborat(1 - ) , cis - [B6H5(CH2)3]- und 1.2-Tetramethylenpentahydro-closo-Hexaborat(1-), cis-[B6H5(CH2)4]- sowie Kristallstrukturen von [P(C6H5)4][B6H5(CH2)3] und [P(C6H5)4][B6H5(CH2)4] / Preparation, 11B, 13C, 1H NMR and Vibrational Spectra of 1.2-Trim ethylenepentahydro-closo-hexaborate(1-), cis-[B6H5(CH2)3]-, and 1.2-Tetramethylenepentahydro-closo-hexaborate(1-), cis-[B6H5(CH2)4]-, and the Crystal Structures of [P(C6H5)4][B6H5(CH2)3] and [P(C6H5)4][B6H5(CH2)4]

1994 ◽  
Vol 49 (8) ◽  
pp. 1115-1122 ◽  
Author(s):  
W. Lübbe ◽  
A. Franken ◽  
W. Preetz
Keyword(s):  
Crystal Structures ◽  
1H Nmr ◽  
Exchange Chromatography ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Nmr Spectrum ◽  
Triclinic Space Group ◽  
Space Group ◽  
H Nmr ◽  
Diethylaminoethyl Cellulose

By reaction of [B6H6]2- with diiodopropane or diiodobutane in dichloromethane the 1,2- rimethylene-pentahydro-closo-hexaborate(1-), cis-[B6H5(CH2)3]-, and the 1,2-tetra-methylene- entahydro-closo-hexaborate(1-), dv-[B6H5(CH2)4]- are obtained, respectively. The compounds were separated from excess [B6H6]2- by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structures of [P(C6H5)4][B6H5(CH2)3] (I) and [P(C6H5)4][B6H3(CH2)4] (II) have been determined by single crystal X-ray diffraction analy­sis: I is triclinic, space group P1̅ with a = 7,388(2), b = 12,254(2), c = 14,415(2) Å, α = 85,638(12)°, β= 84,06(2)°, γ = 85,13(2)°; II is monoclinic, space group P21/c with a =9,7855(10), b = 11,0793(10), c = 25,2386(10) Å, β= 2,491(10)°. The 11B NMR spectra of oth compounds reveal the feature of a cis-disubstituted octahedral B6 cage. The 13C NMR pectrum of I exhibits a quartet at 15,46 ppm with 1J(C,B) = 121,7 Hz (B-CH2) and a triplet at 37,98 ppm with 1J(C,H) = 124,4 Hz (CH2). For II a quartet at 12,89 ppm with 1J(C,B) = 105,5 Hz (B-CH2) and a triplet at 30,00 ppm with 1J(C,H) = 124,4 Hz (CH2) are observed. In the 1H NMR spectrum of I two multiplets at 0,73 and 1,90 ppm of the CH2 groups and two singlets at 2,23 and -3,71 ppm of the BH fragments are bserved; the signals of the CH2 groups of II are at 0,60 and 1,35 ppm and of the BH fragments at 2,15 and -4,81pm,respectively. The IR and Raman spectra exhibit five very strong CH stretching bands between 2807 and 2938 cm-1 in case of I and between 2817 and 2889 cm 1 in case of II.

The Dichloroplatinum(II) and Dichloropalladium(II) Complexes of 1,4-Diazacycloheptane: Preparative, Structural and Conformational Studies

1996 ◽  
Vol 49 (12) ◽  
pp. 1301 ◽  
Author(s):  
GW Allen ◽  
ECH Ling ◽  
LV Krippner ◽  
TW Hambley
Keyword(s):  
Crystal Structures ◽  
Chelate Ring ◽  
Chair Conformation ◽  
Monoclinic Space Group ◽  
Boat Conformation ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
Membered Chelate Ring ◽  
Alternative Conformation

The preparation and purification of [Pt( hpip )Cl2] and [Pd( hpip )Cl2] ( hpip = homopiperazine = 1,4-diazacycloheptane) are described. Crystal structures of [Pt( hpip )Cl2] and [Pd( hpip )Cl2] have been determined by X-ray diffraction methods and refined to R values of 0.023 (932 F) and 0.023 (948 F). The crystals of [Pt( hpip )Cl2] are orthorhombic, space group Pbcm , a 7.7019(8), b 9.8080(12), c 12.1944(14) Ǻ, and those of [Pd( hpip )Cl2] are monoclinic, space group P21/m, a 6.1001(9), b 11.527(2), c 6.458(I) Ǻ, β 106.30(2)°. The seven- membered rings of the ligands in both complexes adopt boat-like conformations in which the five- membered chelate ring has an eclipsed N-C-C-N group and the six- membered chelate ring adopts a chair conformation. Molecular mechanics methods were used to investigate whether this conformation was a crystallographic artefact but it was found to be real. An alternative conformation in which the six-membered chelate ring adopts a skew-boat conformation was also investigated. It was found to be less stable than the conformation observed in the crystal structures, but to a degree that depends on whether non-bonded interactions involving the metal atom were included or not.

Darstellung von Mononitropentahydrohexaborat(2-) und Kristallstruktur von M2[B6H5(NO2)], M = K, Cs / Preparation of Mononitropentahydrohexaborate(2—) and Crystal Structure of M2[B6H5(NO2)], M = K, Cs

1993 ◽  
Vol 48 (12) ◽  
pp. 1727-1731 ◽  
Author(s):  
A. Franken ◽  
W. Preetz ◽  
M. Rath ◽  
K.-F. Hesse
Keyword(s):  
Crystal Structure ◽  
Ion Exchange ◽  
Ion Exchange Chromatography ◽  
Exchange Chromatography ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Dichloromethane Solution ◽  
Space Group ◽  
X Ray ◽  
Diethylaminoethyl Cellulose

By electrochemical oxidation of [B6H6]2- in the presence of nitrite ions and the base DBU in dichloromethane solution mononitropentahydrohexaborate [B6H5(NO2)]2- ions are formed and can be isolated by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structures of the K and Cs salt were determined from single crystal X-ray diffraction analyses. K2[B6H5(NO2)] is monoclinic, space group P21/m with a = 5.953(1), b = 8.059(4), c = 8.906(1) Å, β = 109.553(9)°; Cs2[B6H5(NO2)] is monoclinic, space group P21/a with a = 9.438(6), b = 9.644(7), c = 11.138(9) Å, β = 101.44(9)°. The B6 octahedron is compressed in the direction of the B—NO2 bond by about 5%, with bond lengths between 1.67 and 1.77 A.

Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von cis-[ReCl4X2]2-, X = NCS, NCSe / Crystal Structures, Vibrational Spectra and Normal Coordinate Analysis of cis-[ReCl4X2]2-, X = NCS, NCSe

1998 ◽  
Vol 53 (11) ◽  
pp. 1329-1334 ◽  
Author(s):  
L. Homolya ◽  
S. Strueß ◽  
W. Preetz
Keyword(s):  
Crystal Structures ◽  
Normal Coordinate Analysis ◽  
X Ray Diffraction ◽  
Normal Coordinate ◽  
Triclinic Space Group ◽  
Valence Force ◽  
Space Group ◽  
X Ray ◽  
Valence Force Field ◽  
Ir And Raman

The crystal structures of cis-(n-Bu4N)2[ReCl4(NCS)2] (triclinic, space group P1̅, a = 11,245( 1), b = 20.174(3), c = 21.320(8) Å, a =109.06(2), β = 96.46(2), γ = 98.22(5)°, Z = 4) and cis-(Ph4P)2[ReCl4(NCSe)2]·2CH2Cl2 (triclinic, space group P1̅, a = 10.341(2), b = 13.436(3), c = 19.616(4) Å, α = 92.70(2), β = 92.02(2), γ = 89.99( 1)°, Z= 2) have been determined by single crystal X-ray diffraction analysis. Both ambidentate ligands NCS and NCSe are bonded via the N atom. Using the molecular parameters of the X-ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu4N) salts have been assigned by normal coordinate analysis based on a modified valence force field. The valence force constants fd(ReN) are 1,78(NCS) and 1,79(NCSe) mdyn/ Å.

The Crystal Structures of Et2Sn(O2PMe2)2 and Ph2Sn(O2PMe2)2; Synthesis and Spectral Studies of Ph2Sn(O2PMe2)2

1997 ◽  
Vol 52 (5) ◽  
pp. 587-592 ◽  
Author(s):  
Abdel-Fattah Shihada ◽  
Frank Weller
Keyword(s):  
Structural Information ◽  
Layer Structure ◽  
Chain Structure ◽  
Spectral Studies ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Space Group ◽  
Polymeric Layer ◽  
In Trans ◽  
Ir And Raman

Abstract Ph2Sn(O2PMe2)2 has been synthesized by the reaction of HO2PMe2 with Ph2SnO in toluene or by treating HO2PMe2 with Ph2SnCl2 in methanol. X-ray diffraction studies of Et2Sn(O2PMe2)2 and Ph2Sn(O2PMe2)2 show that the O2PMe2 ligands function as bidentate bridges between the tin atoms. The ethyl and the phenyl groups are in trans-position in the resulting octahedral environment around tin. Et2Sn(O2PMe2)2 crystallizes in the monoclinic space group P21/n (a = 817.11(9), b = 974.1(1), c = 970.1(1) pm, β = 113.749(6)°, Z = 2 and R = 0.032) and con­sists of a polymeric layer structure with centrosymmetric (SnOPO)4 sixteen-membered rings. Ph2Sn(O2PMe2)2 also crystallizes monoclinically in the space group P21/n (a= 1060.9(1), b = 999.4 (1), c = 1768.9(2) pm, β = 90.93(1)°, Z = 4 and R = 0.057) and has a polymeric ring-chain structure with centrosymmetric (SnOPO)2 eight-membered rings. The IR and Raman spectra of Ph2Sn(O2PMe2)2 have been assigned and discussed in the light of structural information. The Sn(O2PMe2)+ ion represents the base peak in the mass spectrum of Ph2Sn(O2Me2)2.

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