Dppa als Komplexligand: Metall-Koordination und P-N-Spaltung in Komplexen des Typs [CpM(L)dppa]X (M = Fe, Mn; L = CO, NO) / Dppa as a Ligand: Metal Coordination and P-N Cleavage in Complexes of the Type [CpM(L)dppa]X (M = Fe, Mn; L = CO, NO)

1997 ◽  
Vol 52 (5) ◽  
pp. 593-603 ◽  
Author(s):  
Jan Geicke ◽  
Ingo-Peter Lorenz ◽  
Petra Mürschel ◽  
Kurt Polbom

Abstract The reactions of [CpMn(CO)2(NO)]BF4 or CpFe(CO)2Cl with PPh2NHR (R = Ph, PPh2) lead to the salts [CpML(CO)PPh2NHR]X with monodentate aminophosphine ligands. In the case of R = PPh2 (= dppa) the complexes [CpML(dppa)]X with bidentate dppa are also formed. The salt [CpFe(CO)(dppa)]Cl can be deprotonated to give the neutral complex CpFe(CO){(PPh2)2N)} with the diphosphinoamide ligand, which can be N-alkylated by Mel to afford [CpFe(CO){(PPh2)2NMe}]I. The complex [CpMn(NO)(dppa)]BF4 undergoes a P-N cleavage reaction by the solvent methanol to form [CpMn(NO)(PPh2NH2)(PPh2OMe)]BF4. The non-chelated complexes [CpFe(CO)2PPh2NHR]Cl are deprotonated by DBU to give the neutral ferrioiminophosphoranes CpFe(CO)2PPh2 = NR. For R = PPh2 photolysis leads to CO-elimination and to CpFe(CO)(PPh2NPPh2). CpFe(CO)2PPh2NPPh2 can be alkylated by Mel or metallated by CpFe(CO)2Cl to form [CpFe(CO)2PPh2NPPh2Me]I or [CpFe(CO)2PPh2NPPh2(CO)2FeCp]Cl, respectively. Oxidation of CpFe(CO)2PPh2NPPh2 is possible by (SiMe3)2O2, sulfur, or selenium to lead to the neutral complexes CpFe(CO)2PPh2=NPPh2 = E (E = O, S, Se) with a heterodiene system. The IR and NMR spectra of all species as well as the X-ray structures of the complexes [CpFe(CO)dppa]Cl, [CpMn(NO)dppa]BF4 and [CpMn(NO)(PPh2NH2)(PPh2OMe)]BF4 are reported and discussed.

2007 ◽  
Vol 62 (2) ◽  
pp. 244-248 ◽  
Author(s):  
Li Baolin ◽  
Guo Jian ◽  
Zhang Xiquan ◽  
Lai Yitian ◽  
Hu Huaiming

Several new 4’-O-substituted derivatives of 3,4,5-trimethoxy-4’-hydroxystilbene were synthesized and characterized by their IR and NMR spectra. The crystal structure of ethyl {4-[(E)-2-(3,4,5-trimethoxyphenyl) vinyl]phenoxy}acetate, one of these stilbene derivatives, has been solved by singlecrystal X-ray structure analysis. The results show that all carbon and oxygen atoms in the molecule are nearly coplanar except C(16), and molecules stack to a column arrangement owing to C-H···π interactions. Pairs of these columns are linked by other molecules, and these linker molecules themselves also produce a column along the other direction. A puckered cyclic tetramer R44 (46) is formed and the tetramer propagates itself via intermolecular hydrogen bonds and C-H···π interactions. In this way, molecules are interrelated and assembled to a two-dimensional layer structure.


1983 ◽  
Vol 38 (3) ◽  
pp. 373-377 ◽  
Author(s):  
Christian Burschka ◽  
Eyup Akgün ◽  
Ulf Pindur

AbstractThe structures of 1a-1d were investigated by spectroscopic methods and in the case of la in addition by X-ray diffraction, 1a, vicarious for the compounds 1, is stabilized in solution and in the crystal by an intramolecular hydrogen bond in an eight-membered ring. The IR and NMR spectra show that 1 exhibit a symmetrical structure. In the case of 1 a the molecular structure is affected by unsymmetrical packing and electrostatic effects in the crystal and is therefore approximated best between the forms I and II.


1987 ◽  
Vol 42 (6) ◽  
pp. 739-745 ◽  
Author(s):  
Max Herberhold ◽  
Bertram Schmidkonz ◽  
Manfred L. Ziegler ◽  
Orhan Serhadle

Abstract Reaction of the tetrahydrofuran-stabilized 16-electron complex fragment [Cp*Re(CO)2] with dimethyl disulfide, MeSSMe, leads to the diamagnetic title compound, Cp*Re(CO)(SMe)2 , which was characterized by mass, IR and NMR spectra and by an X-ray crystal structure analysis**. The two methylsulfido ligands are bent (angles Re-S-CH3 114.1(3)°) and turned away from the Cp* ring. The Re - S-bond distances are 227.0(2) pm.


2020 ◽  
Vol 24 (10) ◽  
pp. 1139-1147
Author(s):  
Yang Mingyan ◽  
Wang Daoquan ◽  
Wang Mingan

2-Phenylcyclododecanone and 2-cyclohexylcyclododecanone derivatives were synthesized and characterized by 1H NMR, 13C NMR, HR-ESI-MS and X-ray diffraction. Their preferred conformations were analyzed by the coupling constants in the 1H NMR spectra and X-ray diffraction, which showed the skeleton ring of these derivatives containing [3333]-2-one conformation, and the phenyl groups were located at the side-exo position of [3333]-2-one conformation due to the strong π-π repulsive interaction between the π- electron of benzene ring and π-electron of carbonyl group. The cyclohexyl groups were located at the corner-syn or the side-exo position of [3333]-2-one conformation depending on the hindrance of the other substituted groups. The π-π electron effect played a crucial role in efficiently controlling the preferred conformation of 2-aromatic cyclododecanone and the other 2-aromatic macrocyclic derivatives with the similar preferred square and rectangular conformations.


1981 ◽  
Vol 46 (10) ◽  
pp. 2345-2353 ◽  
Author(s):  
Karel Baše ◽  
Bohumil Štíbr ◽  
Jiří Dolanský ◽  
Josef Duben

The 6-N(CH3)3-6-CB9H11 carbaborane reacts with sodium in liquid ammonia with the formation of 6-CB9H12- which was used as a starting compound for preparing the 4-CB8H14, 9-L-6-CB9H13 (L = (CH3)2S, CH3CN and P(C6H5)3), 1-(η5-C5H5)-1,2-FeCB9H10-, and 2,3-(η5-C5H5)2-2,31-Co2CB9H10- carboranes. The 4-CB8H14 compound was dehydrogenated at 623 K to give 4-(7)-CB8H12 carborane. Base degradation of 6-N(CH3)3-6-CB9H11 in methanol resulted in the formation of 3,4-μ-N(CH3)3CH-B5H10. The structure of all compounds was proposed on the basis of their 11B and 1H NMR spectra and X-ray diffraction was used in the case of the transition metal complexes.


1998 ◽  
Vol 63 (2) ◽  
pp. 211-221 ◽  
Author(s):  
Miloš Tichý ◽  
Luděk Ridvan ◽  
Miloš Buděšínský ◽  
Jiří Závada ◽  
Jaroslav Podlaha ◽  
...  

The axially chiral bis(α-amino acid)s cis-2 and trans-2 as possible building blocks for polymeric structures of novel type of helicity were prepared. Their configuration has been determined by NMR spectroscopy and, in the case of the trans-isomer, confirmed by single-crystal X-ray diffraction. Analogous pair of stereoisomeric diacids cis-3 and trans-3, devoid of the amino groups, was also prepared and their configuration assigned. The observed differences in the NMR spectra of cis- and trans-isomers of 2 and 3 are discussed from the viewpoint of their different symmetry properties.


1997 ◽  
Vol 62 (5) ◽  
pp. 746-751 ◽  
Author(s):  
Andreas Franken ◽  
Jaromír Plešek ◽  
Christiane Nachtigal

On treatment of the [(1,2-C2B9H11)2Co]- ion with naphthalene in presence of AlCl3 a remarkably bridged [8,8'-μ-(CH2-C9H6)-(1,2-C2B9H10)2-3-Co]- ion is obtained as a single isolated compound. The triatomic -CH2-C9H6- bridge is derived from the rearranged naphthalene nucleus. The mechanism of this reaction is obscure but it does resemble the "Electrophile-Induced Nucleophilic Substitution" reported earlier. The structure of the compound was established by multinuclear NMR spectroscopy and by single crystal X-ray diffraction.


2020 ◽  
Vol 75 (9-10) ◽  
pp. 851-857
Author(s):  
Chong Chen ◽  
Fule Wu ◽  
Jiao Ji ◽  
Ai-Quan Jia ◽  
Qian-Feng Zhang

AbstractTreatment of [(η6-p-cymene)RuCl2]2 with one equivalent of chlorodiphenylphosphine in tetrahydrofuran at reflux afforded a neutral complex [(η6-p-cymene)RuCl2(κ1-P-PPh2OH)] (1). Similarly, the reaction of [Ru(bpy)2Cl2·2H2O] (bpy = 2,2′-bipyridine) and chlorodiphenylphosphine in methanol gave a cationic complex [Ru(bpy)2Cl(κ1-P-PPh2OCH3)](PF6) (2), while treatment of [RuCl2(PPh3)3] with [2-(C5H4N)CH=N(CH2)2N(CH3)2] (L1) in tetrahydrofuran at room temperature afforded a ruthenium(II) complex [Ru(PPh3)Cl2(κ3-N,N,N-L1)] (3). Interaction of the chloro-bridged complex [Ru(CO)2Cl2]n with one equivalent of [Ph2P(o-C6H4)CH=N(CH2)2N(CH3)2] (L2) led to the isolation of [Ru(CO)Cl2(κ3-P,N,N-L2)] (4). The molecular structures of the ruthenium(II) complexes 1–4 have been determined by single-crystal X-ray crystallography. The properties of the ruthenium(II) complex 4 as a hydrogenation catalyst for acetophenone were also tested.


Polyhedron ◽  
1986 ◽  
Vol 5 (11) ◽  
pp. 1741-1746 ◽  
Author(s):  
Gerard Lawless ◽  
Gerard McNally ◽  
A.R. Manning ◽  
Desmond Cunningham ◽  
Patrick McArdle
Keyword(s):  
1H Nmr ◽  

1997 ◽  
Vol 36 (22) ◽  
pp. 4968-4982 ◽  
Author(s):  
Yangzhen Ciringh ◽  
Scott W. Gordon-Wylie ◽  
Richard E. Norman ◽  
George R. Clark ◽  
Susan T. Weintraub ◽  
...  

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