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.

Z. Naturforsch. 51 b, 681-685 (1996); received August 28, 1995 Molybdenum-chalcogenido Complexes, Nitrosyl Compounds, X-Ray The reactions of hydrido-tri(3,5-dimethyl-l-pyrazolyl)borate nitrosylmolybdenum diiodide, Tp*Mo(NO)L (2), with the oligochalcogenides (NH^Sio and (NEuteSeö in THF solution lead to mononuclear cvc/o-pentachalcogenido complexes, Tp*Mo(NO)(E5) (E = S (3a), Se (3b)). In the presence of either H2S or H^Se (generated by slow “in situ” hydrolysis of AI2E3 in moist THF solution) 2 is converted into binuclear chalcogenido-bridged products, Tp2Mo2(NO)2(//-E)2 (E = S (4a), Se (4b)) which are more conveniently obtained from 3a,b by dechalcogenation with tri(''butyl)phosphane (1:4,5). The new chalcogen complexes 3a,b and 4a,b were characterized by IR, NMR and mass spectroscopy and compared with the related chalcogen compounds derived from pentamethylcyclopentadienyl nitrosylmolybdenum diiodide, Cp*Mo(NO)l2. The molecular structure of Tp*Mo(NO)(Ses) (3b) has been determined; the complex contains a sixmembered MoSe«; metallacycle in the chair conformation and a linearly coordinated nitrosyl ligand (angle M o-N -0 178.9(17)°).

für Naturforschung in cooperation with the Max Planck Society for the Advancement of Science under a Creative Commons Attribution 4.0 International License. Dieses Werk wurde im Jahr 2013 vom Verlag Zeitschrift für Naturforschung in Zusammenarbeit mit der Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. digitalisiert und unter folgender Lizenz veröffentlicht: Creative Commons Namensnennung 4.0 Lizenz. Application of Reverse Two-Dimensional ^ { ^ N } NMR Spectroscopy to the Characterization of Two Inorganic Compounds: (CO)5Cr^(R)NSNSNH

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.

Three series of ferrocenes, derived from aminoferrocene Fc-NH2 and 1,1'-diaminoferrocene fc(NH2)2, were studied by 57Fe NMR spectroscopy. A marked decrease in 57Fe magnetic nuclear shielding with respect to ferrocene is observed if the nitrogen atom becomes part of a pi-acceptor linked to one or both cyclopentadienyl rings. In contrast, pi-donor properties of the amino group(s) affect delta57Fe to a much smaller extent. In the case of the fairly rigid structures of 1,3-diaza-2-element-[3]ferrocenophanes, a significant increase of 57Fe nuclear magnetic shielding is observed, in contrast to the corresponding [n]ferrocenophanes with n > 3. Structures of numerous of the ferrocene derivatives have been optimized for the gas phase by calculations (B3LYP/6-311 + G(d,p) level of theory), and 57Fe nuclear magnetic shieldings were calculated using these geometries. There is reasonable agreement in the trends for experimental and calculated data.

Isocyanato- (1a), 1,1'-di(isocyanato)- (2a), isothiocyanato- (1b), 1,1'-di(isothiocyanato)- (2b), isoselenocyanato- (1c) and 1,1'-di(isoselenocyanato)ferrocene (2c) were prepared and studied by H-1, C-13 and N-14 NMR spectroscopy. Isocyanatoferrocene (1a) trimerizes upon chromatography on alumina to give 3a. The molecular structures of 2c and 3a were determined by X-ray analysis, and almost undistorted ferrocene-like structures were found in both cases.

Brown crystals of [PPh4](2)[Se2Br6] (1) and [PEtPh3](2)[Se2Br6] (2) were obtained when selenium and bromine reacted in acetonitrile Solution in the presence of tetraphenylphosphonium bromide and ethyltriphenylphosphonium bromide, respectively. The crystal structure of 2 has been determined by Xray methods and refined to R = 0.0420 for 4161 reflections. The crystals are monoclinic, space group P2(1)/n with Z = 2 and a = 13.055(3) angstrom, b = 12.628(3) angstrom, c = 13.530(3) angstrom, beta = 92.40(3)degrees (293(2) K). In the solid state structure of 2 the dinuclear hexabromo-diselenate(II) anion is centrosymmetric and consists of two distorted almost square-planar SeBr4 units sharing a common edge through two bridging Br atoms. The terminal Se-II-Br bond distances are found to be 2.419(1) and 2.445(1) angstrom, the bridging mu Br - Se-II bond distances 2.901(1) and 2.802(1) angstrom.

The shortening of partly multiple M–Te (M = Mn, Fe, Co, Cr or W) bonds is observed for two classes of organometallic compounds: (1) formally electron-deficient species with additional donor–acceptor interaction between Te lone pairs and half-occupied d-orbitals of M; (2) formally electron-saturated species having additional dative interaction between M lone pairs and LUMO of Te. These compounds could be prepared by two main methods: (a) interaction of [CpMn(CO)2PhC(O)−]Li+ with Te proceeds via formation of intermediate {[CpMn(CO)2]2Te}2− which is further transformed into binuclear complex [CpMn(CO)2]2Te(CH2Ph)2 or into trinuclear ditelluride cluster [CpMn(CO)2]3Te2 on one hand or to mixed-metal monotelluride clusters [CpMn(CO)2]2TeM(CO)5 on another hand. (b) treatment of Fe(CO)5, CpMn(CO)2(THF) or Me4C4Co(CO)2I with [PhTeI]4, PhTeI3 or PhTeI2HC = CPhI results in different PhTeI-containing complexes of Fe, Mn or Co. The molecular structures of all new compounds were studied by means of X-ray diffraction analyses and the mechanism of M–Te bond shortening is discussed.

Recent results are summarized on some new aspects of the main group chemistry of the 1,2- diselenido-1,2-dicarba-closo-dodecaborane(12) dianion 3, (1,2-(1,2-C2B10H10)Se2) 2- . The reactions of 3 with organoelement-Group 14 dichlorides (Ph2CCl2, Me2SiCl2, Ph2SiCl2, Me2SnCl2, Ph2SnCl2) and phenylphosphorus dichloride (PhPCl2) afforded novel five-member heterocycles along with other products. In the case of Ph2SiCl2, the expected product 6 was accompanied by another five-member ring 8 containing the Ph2Si-Se-Se moiety. The phospholane 13 could be oxidised to the sulfide 14 and the selenide 15, and partial hydrolysis gave the selenophosphonic acid 16 along with the bis(diselane) 18 and decomposition. The dianion 3 was converted by oxidative coupling into the bis(diselane) 18, an eight-member ring with annellated carborane moieties. Symmetric cleavage of this ring in 18 took place by oxidative addition of 18 to bis(triphenylphosphane)ethene-platinum(0) to give the (Ph3P)2Pt(II) complex 20 with the chelating 1,2-diselenido-1,2-dicarba-closo-dodecaborane(12) ligand. Oxidative addition of the five-member heterocycles containing Se-Sn-Se fragments (9, 11) to bis(triphenylphosphane)ethene-platinum(0) proceeded at low temperature by insertion of the (PPh3)2Pt fragment into one of the Sn-Se bonds (21, 22). The reaction of 11 with bis(triphenylphosphane)ethene-platinum(0) took place by oxidative addition of the P-Se bond, followed by rearrangement (25). The molecular structures of the five-member rings with annellated carborane units 4 (CPh2), 11 (SnPh2), 13 (PPh), 14 (PhP=S), 20 (Pt(PPh3)2, and of the bis(diselane) 18 were determined by X-ray analyses.The proposed solution-state structures of the new compounds followed from consistent sets of multinuclear magnetic resonance data ( 1 H, 11 B, 13 C, 29 Si, 31 P, 77 Se, 119 Sn and 195 Pt NMR).

Lithiation of 1,2-dicarba-closo-dodecaborane(12) (1) followed by insertion of selenium into both C-Li bonds leads to the 1,2-diselenolato-1,2-dicarba-closo-dodecaborane(12) dianion (3), which is converted by oxidative coupling into the cyclic eight-membered bis(diselane) 4 with annellated carborane moieties. Oxidative addition of 4 to ethenebis(triphenylphosphane) platinum (0) gives the bis(triphenylphosphane)platinum(II) complex 7, which contains a chelating 1,2-diselenol-ato-1,2-dicarba-closo-dodecaborane(12) ligand, by symmetric cleavage of the eight-membered ring in 4 and displacement of ethene. The molecular structures of 4 and 7 were determined by X-ray analysis. The solution-state structures of the new compounds are supported by multinuclear NMR data(H-1, B-11, C-13, Si-29, P-31, Se-77, Pt-195). (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007.

C14H20B10P2Se3, monoclinic, P12(1)/n1 (no. 14), a = 13.384(1) angstrom, b= 11.128(1) angstrom, c = 17.955(1) angstrom beta = 122.979(6)degrees, V 2243.3 angstrom, Z = 4, R-gt(F) = 0.043, wR(ref)(F-2) = 0.079, T = 191 K.

1‐Cyclohepta‐2,4,6‐trienyl‐selanes Se(C7H7)2 (2c), RSeC7H7 with R = Bu, tBu, Ph, 4‐FC6H4 (12a,b,c,d) were prepared by the reaction of the corresponding silanes, Si(SeMe3)2 and RSeSiMe3, respectively, with tropylium bromide C7H7Br. In spite of the low stability of the selanes even in dilute solutions and at low temperature, they could be characterised by their 1H, 13C and 77Se NMR parameters. Coupling constants 1J(77Se,13C) were measured and calculated by DFT methods at the B3LYP/6‐311+G(d,p) level of theory. The comparison of experimental and calculated coupling constants 1J(77Se,13C) included numerous selenium carbon compounds with largely different SeC bonds, revealing a satisfactory agreement. Both the spin–dipole (SD) and the paramagnetic spin‐orbital (PSO) terms contributed significantly to the spin–spin coupling interaction, in addition to the Fermi contact (FC) term. Copyright © 2006 John Wiley & Sons, Ltd.

The reaction of the 1,2-diselenido-1,2-dicarba-closo-do-decaborane dianion (1) with dichloro(phenyl)phosphane affords the 1,3,2-discienaphospholane (2) containing an anellated dicarbacloso-docecaborane(12) unit. The phospholane 2 was oxidised by reactions with the elements to the sulfide 3 and the selenide 4, and partial hydrolysis gave a selenophosphonic acid derivative 5 along with the bis(diselane) 6 and decomposition. The reaction of 2 with (ethene)bis(triphenylphosphane)platinum(0) displaces ethene and is accompanied by oxidative addition and rearrangement into the bis(triphenylphosphane)platinum(I I) complex 9, in which the chelating unit is linked to platinum via Pt-Se and Pt-P(Se) bonds, a rare example of a metallophosphane selenide. The molecular structures of 2 and 3 were determined by X-ray analysis. The solution-state structures of the new compounds follow from consistent multinuclear magnetic resonance data (H-1, B-11, C-13, P-31, Se-77, Pt-195 NMR).

The reactions of the 1,2-diselenolato-1,2-dicarba-closo-dodecaborane(12) dianion 1 with diorganoelement(IV) dichlorides (Ph 2 CCl 2 , Me 2 SiCl 2 , Ph 2 SiCl 2 , Me 2 SnCl 2 , Ph 2 SnCl 2 ) gave novel five-member heterocycles along with other products. The molecular structures of the five-member rings containing CPh 2 (2) and SnPh 2 (9) moieties between the selenium atoms were determined by X-ray analyses. In the case of the chlorosilanes, the analogous five-member ring containing the SiPh 2 unit (4) could be identified in mixtures. The expected reaction was accompanied by rearrangement leading to formation of another five-member ring 6 containing the Ph 2 Si-Se-Se moiety. Oxidative addition of the five-member heterocycles containing tin (7, 9) to ethene-bis(triphenylphosphane)platinum(0) gave at low temperature the bis(triphenylphosphane)platinum(II) complexes 12 and 13, where the Pt(PPh 3 ) 2 fragment had been inserted into one of the Sn-Se bonds. Extensive decomposition of these complexes was observed above -20 °C. The proposed solution-state structures of the new compounds are supported by multinuclear magnetic resonance data ( 1 H, 11 B, 13 C, 29 Si, 31 P, 77 Se, 119 Sn and 195 Pt NMR).

Dimetallic complexes {Cp* Ir[E2C2(B9H9)][(cod) Ir(OCH3)]} (E = S, 3a; E = Se, 3b) and {Cp* Ir[E2C2( B10H9)][(cod) Ir]} (E = S, 4a; E = Se, 4b) were synthesized by the reaction of half-sandwich complexes Cp* Ir[E2C2(B10H10)] (E = S, 1a; Se, 1b) with 2 equiv of [Ir(cod)(mu-OMe)](2) (2-Ir). Analogous reactions of 1a with [Rh(cod)(mu-OMe)] 2 (2-Rh) were investigated, and three complexes, {Cp* Ir[S2C2(B9H9)][(cod)Rh( OCH3)]} (5a), {Cp* Ir[S2C2(B10H10)][(cod) Rh]} ( 6a), and {Cp* Ir[S2C2(B10H9)][(cod) Rh]} ( 7a), were obtained. By comparing the two reactions, the routes of metal-induced B-H activation at B(3)/B(6) of the ortho-carborane-1,2-dichalcogenolato ligand were investigated. These nido-carborane complexes such as 3a, 3b, and 5a contain intercluster metal-metal bonds. Moreover, the V-shaped trimetallic units {( cod) Ir[E2C2(B9H8)][(cod) Ir(OCH3)][(C8H13) Ir]} (E = S, 9a; Se, 9b) have been constructed through the M-2-nido-carborane complexes {(cod) Ir[E2C2(B9H9)][(cod) Ir(OCH3)]} (E = S, 8a; Se, 8b). Complexes 3- 10 were characterized by NMR spectroscopy (H-1, B-11 NMR), and X-ray structural analyses were reported for complexes 3a, 3b, 4a, 5a, 6a, 8a, 9b, and 10b.

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.

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.

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.

The intramolecular dynamic behavior of the tetrahedrane-type cluster [Fe 2 (CO) 6 (μ-SNH)] 1 was studied by 13 C NMR spectroscopy. The 57 Fe chemical shift of 1 and the coupling constants 1 J ( 57 Fe, 13 C) were measured. These NMR parameters, and also 1 J ( 57 Fe, 15 N), were found to be in good agreement with data calculated by using density functional theory (DFT) methods (B3LYP), based on the geometry calculated at the 6-311+G(d,p) level of theory. The isolobal replacement of the Fe(CO) 3 with BH fragments leads to the tetrahedranes [Fe(CO) 3 (BH)(μ-SNH)] 2 and [(HB) 2 (μ-SNH)] 3 . Both were identified by calculations as minima on the respective potential energy surface (PES). However, the tetrahedrane-type structure of 3 is much higher in energy when compared with the planar cyclic isomers 3a and 3b .

The insertion of tellurium into the carbon-lithium bonds of lithiated ortho-carborane, C2B10H12, in solution can be used to generate organometallic derivatives with Te2 units. In addition to di(ortho-carborane-1-yl) ditellane, (C2B10H11)2Te2 (2c), two cylic compounds containing each two annellated [(dicarba-closo-dodecaborano)] units, (C2B10H10)2Te4 (3c) and (C2B10H10)2Te2(SnMe2) (4c), have been structurally characterized.