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  • Chemistry  (12)
  • 1-Organo-1-aza-closo-dodecaborane(12)  (1)
  • Conformational analysis  (1)
  • 1
    Electronic Resource
    Electronic Resource
    1,3-Addition von Aziden an Azadecaboran: 6-Azadecaboran-4,9-diyltriazene (1992)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 2025-2026 
    Details
    ISSN: 0009-2940
    Keywords: Aza-nido-decaborane(12) ; (1H-Triazen-1,3-diyl)-aza-arachno-decaborane(13) ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,3-Addition of Azides to Azadecaborane: 6-Azadecaborane-4,9-diyltriazenesnido-NB9H12 (1) reacts with azides RN3 to form a coordinative B-N bond between B9 and N1 of RN3, accompanied by the α-addition of the B4-H bond of 1 to the N3 atom of RN3. The products 2a, b (R = H, CH2Ph, respectively) thus contain an azadecaborane skeleton and a five-membered unsaturated B2N3 ring with a common B-B edge. The product 2a crystallizes in the space group Pna21.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19921250909
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  • 2
    Electronic Resource
    Electronic Resource
    Dimeric Silver(I) Complexes of Some Isothiazole-Based LigandsDedicated to Prof. Dr. Rolf Gleiter on the occasion of this 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 95-100 
    Details
    ISSN: 0009-2940
    Keywords: Isothiazole complexes ; Dinuclear silver(I) complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of isothiazole-based potential ligands bearing substituents with additional donor sites in the 5-position of the heterocycle was synthesized [3-Me-5-R-C3HNS; R = CH=N(CH2)2py (1), CH=NCH2py (2), CH2N(CH2CH2NEt2)2 (4), (CH2)2SMe (5)]. Upon reaction with AgO3SCF3 they formed complexes [(1)AgOSO2CF3]2 (6), [(2)AgOSO2CF3]2 (7), [(4)Ag]2+2(O3SCF-3)2 (8) and [(5)AgOSO2CF3]2 (9), respectively. 6, 8 and 9 were shown by X-ray structural analyses to consist of dimeric units L2Ag2+2, either discrete (8), coordinated by terminal CF3SO-3 units (6). In 8 and 9 the isothiazole moiety is bonded to the metal center via the ring-N. The coordination potential of the isothiazole heterocycle is discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300115
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  • 3
    Electronic Resource
    Electronic Resource
    Pyrazolate-Based Oligonuclear Copper and Silver Complexes with N/S Coordination SpheresDedicated to Prof. Dr. Gottfried Huttner on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1441-1447 
    Details
    ISSN: 0009-2940
    Keywords: Pyrazolate complexes ; Bridging ligands ; Copper ; Silver ; N,S-Donor Ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of pyrazole-based potential ligands bearing thioether substituents in 3- and 5-positions of the heterocycle was synthesized [3,5-bis(RSCH2)-pyzH R=Ph (1aH), PhCH2 (1bH), iPr (1cH), tBu (1dH)]. These ligands afford oligonuclear Cu1 and Ag1 coordination compounds [LCu]x (2a-c, L = 1a - c) and [LAg]x (3a-d, L = 1a-d), respectively. The single crystal X-ray analysis of 3c shows the presence of trimeric planar arrays of N,N′-bridging pyrazolates and linear coordinated silver ions, with each two of the trinuclear moieties being linked by two unsupported short intermolecular Ag…Ag contacts [3.041(1) Å]. Molecular-weight determinations for 2a (THF) and 3c (toluene) indicate that hexanuclear entities are preserved in solution. Starting from 1bH the CuII complex [(1b)2Cu2](BF4)2 (4) was synthesized. According to an X-ray crystal structure analysis it consists of dinuclear molecules with two bridging pyrazolates, distorted square planar N2S2 coordination spheres for Cu11 and an axially bridging tetrafluoroborate. Magnetic susceptibility data reveal an antiferromagnetic exchange (J = -206 cm-1) that is among the highest found for doubly pyrazolate bridged dicopper(II) complexes, which is rationalized on the basis of the rather symmetric dinuclear core of 4. The irreversibility of the electrochemical reduction and oxidation processes for the CuII and CuI compounds, respectively, is explained by the inability of the respective coordination framework to adapt to different geometric preferences.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301014
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  • 4
    Electronic Resource
    Electronic Resource
    Reaktion von Decaboran mit dem Phosphaalkin PCtBu (1994)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 93-95 
    Details
    ISSN: 0009-2940
    Keywords: Decaborane ; 1-Phosphabutin, 3,3-dimethyl ; Bis(decaboranyl)methane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of Decaborane with the Phosphaalkyne PC tBuThe borane B10H12(SMe2)2 (1) reacts with the phosphaalkyne P°CtBu to form the product [B10H11(SMe2)][C(tBu)-PH](B10H12) (2), in which two B10 units are linked by a HP-CtBu bridge. The B10 unit B is simply bound to the bridge C atom, whereas the B10 unit A is bound to both bridging atoms, P and C, by atom B6 and, moreover, to the P atom by atom B5. The solvate complex 2 · CH2Cl2 crystallizes in the space group P¯.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19941270115
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  • 5
    Electronic Resource
    Electronic Resource
    Zur Thermolyse von Amin - arachno-Nonaboran (1994)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 853-855 
    Details
    ISSN: 0009-2940
    Keywords: Diethylamine - arachno-nonaborane ; Diethylamine - octadecaborane ; conjuncto-Bis[6′5′:5,6]decaborane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the Thermolysis of Amine-arachno-NonaboraneTwo molecules of diethylamine-arachno-nonaborane, B9H13-(NHEt2), undergo a condensation at 140°C to give diethylamine-conjuncto-bis[6′,5′:5,6]decaborane, B18H20(NHEt2) (4). The deprotonation of 4 yields the anion [B18H19(NHEt2)]-which can be crystallized with the cation [NEt3(CH2Ph)]+ (space group P1).
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19941270512
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  • 6
    Electronic Resource
    Electronic Resource
    Dinuclear Cobalt(II) Complexes of Pyrazole Ligands with Chelating Side ArmsDedicated to Prof. Dr. Walter Siebert on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 605-613 
    Details
    ISSN: 0009-2940
    Keywords: Pyrazolate complexes ; Dinuclear complexes ; Bridging ligands ; Cobalt ; Conformational analysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of pyrazole-based potential ligands bearing polydentate amine substituents in the 3- and 5-positions of the heterocycle has been synthesized [3,5-bis(R2NCH2)-pyzH R2N = Me2N(CH2)3NMe (2aH), [Me2N(CH2)3]2N (2bH), (Et2NCH2CH2)2N (2cH)]. Upon reaction with two equivalents of CoCl2 they form complexes LCo2Cl3 (3a-c; L = 2a-c, respectively) which are shown crystallographically to contain a dinuclear metal core bridged by both the pyrazolate unit and a chlorine atom, with each cobalt center carrying a further terminal chlorine atom. Two of the ligand side arms in 3b, c are dangling, thus leading to five-coordination of the cobalt(II) centers in all cases. Addition of two equivalents of NaBPh4 to solutions of 3b, c induced coordination of the formerly dangling side arms to the metal centers by substitution of the terminal chlorine atoms. The resulting compounds [LCo2Cl](BPh4)2 (4b, c, respectively) were characterized by X-ray structure analyses. They can be viewed as dinuclear linked versions of tran-type complexes [(tran = tris(aminoalkyl)amine] with distorted trigonal-bipyramidal coordination spheres around cobalt(II). Conformational analyses employing force-field calculations were carried out for 4b, c in order to rationalize the conformations observed in the solid state with regard to the accessible conformational space.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300511
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  • 7
    Electronic Resource
    Electronic Resource
    1,1-Hydroborierung von Alkinen mit 6-Aza-nido-decaboranen (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 947-951 
    Details
    ISSN: 0009-2940
    Keywords: 6-Aza-nido-decaborane ; 9-(1-Alkenyl)-6-phenyl-6-aza-nido-decaborane ; 1,1-Hydroboration of alkynes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,1-Hydroboration of Alkynes with 6-Aza-nido-decaboranes[1]Alkynes AC≡CR′ (R′ = Me, Bu, tBu, SiMe3), that contain a mobile group A, like H or SiMe3, undergo hydroboration by 6-aza-nido-decaboranes RNB9H11 (1a-c, R = H, Ph, PhCH2) and 1,2-migration of the group A, to give the corresponding 9-(1-alkenyl)-6-aza-nido-decaboranes RNB9H10(CH=CR′A) (2a-h). Ethenes AHC=CH2 (A = SiMe3, SnBu3) are hydroborated by 1a, b as well to form products of the type RNB9H10(CH2CH2A) (3a-c). The alkyne Me3SiC=CH undergoes a hydroboration with 1b twice; the formation of (PhNB9H10)2CHCH2SiMe3 (4) proceeds by a 1,1- and a 1,2-hydroboration step, apparently. The crystal structure analysis of (PhCH2)NB9H10[CH=CMe(SiMe3)] (2e; space group Pl) reveals a (Z configuration of the ethene moiety.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280916
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  • 8
    Electronic Resource
    Electronic Resource
    Öffnung des Aza-closo-dodecaboran-Gerüsts durch Basen (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1225-1229 
    Details
    ISSN: 0009-2940
    Keywords: 1-Organo-1-aza-closo-dodecaborane(12) ; Trialkylamine-1-organo-1-aza-nido-dodecaborane(12) (1/1) ; Undecahydro-1-organo-1-aza-nido-dodecaborate(1-), 2-hydro-, 2-halogeno-, 2-alkoxy-, 2-amino-, 2-alkyl- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Opening of the Aza-clso-dodecaborane Skeleton by BasesThe aza-closo-borane PhNB11H11 (1a) is opened by the amines NR3 (R = Me, Et) to give the novel aza-nido-dodecaboranes PhNB11H11(NR3) (2a, b). The non-planar open pentagonal face of 2a, b accomodates the N atom, a BHB bridge, and the base-bound B atom, according to NMR spectra and the crystal structure analysis of monoclinic 2b. A similar but more symmetric structure is found when closo-RNB11H11 (1a-c, R = Ph, Me, H) is attacked by anionic bases X- to give nido-RNB11H11X- (3a-j; R/X = Me/H, Me/F, Me/Cl, Ph/OH, H/OMe, Me/OMe, Me/OtBu, Me/NEt2, Me/Me, Me/Bu). The anions are precipitated with cations [K([18]crown-6)], [S(NMe2)3], [N(PPh3)2], [Et2NH2], or [Li(tmeda)2]. The nido-structures of type 2 and 3 are derived from the hypothetical closo-NB12H13.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951281214
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  • 9
    Electronic Resource
    Electronic Resource
    Novel μ3-Coordination of Urea at a Nickel(II) Site: Structure, Reactivity and Ferromagnetic Superexchange (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1851-1854 
    Details
    ISSN: 1434-1948
    Keywords: Urea ; Nickel ; Coordination modes ; Cooperative effects ; Magnetic properties ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A tetranuclear mixed-spin nickel(II) complex featuring two urea molecules in an unprecedented μ3-ĸN:ĸN′:ĸO coordination mode has been structurally characterized. The two central high-spin nickel(II) ions exhibit ferromagnetic coupling (J = +3.4 cm-1) mediated by the NH2-C-O linkages of the bridging urea. In solution the temperature dependence of the UV/Vis optical absorption and of the magnetic moment indicate that, upon cooling, additional solvent molecules bind to the terminal low-spin metal ions and a concomitant spin change occurs. In the solid state the coordinated urea ligands can be thermally degraded to cyanate within the grip of the multimetallic nickel(II) site.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Cooperative Binding of Nitrile Moieties Within a Bimetallic Pocket: Enforcing Side-On π-Interaction With a High-Spin Nickel(II) Site (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 771-781 
    Details
    ISSN: 1434-1948
    Keywords: Cooperative effects ; Coordination modes ; Nickel ; Bimetallic complexes ; π interactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Different cooperative binding modes of nitriles within the bimetallic pocket of a pyrazolate-based compartmental dinickel(II) site have been studied. The H3O2-bridged dinuclear complex 1 reacts with cyanamide to yield 4, in which a secondary hydrogencyanamido(1-) bridge spans the two metal centers at an unusually short metal-metal distance imposed by the primary ligand matrix. In 5, a single 2-cyanoguanidine (cnge) molecule is N-bound to one nickel(II) ion through its nitrile part and is coordinated to the adjacent metal site through an amido nitrogen. The characteristics of the coordination spheres of the metal centers suggest an additional side-on π-bonding interaction of the nitrile moiety with the second high-spin nickel(II) ion. This unusual interaction is corroborated by comparing the IR bands for the ν(C≡N) stretching vibration of 5 with those of complex 6, which has two end-on bound cnge molecules, and those of the related mononuclear complex 7, which lacks a second nickel(II) ion. The nature of the π-bonding interaction in 5 is further analyzed by DFT calculations on relevant model systems. Even though the π-bonding is found to be very weak, it does include some backbonding from occupied 3d MOs at the second high-spin nickel(II) ion to the π* MOs of the nitrile. Such an unconventional π-interaction is suggested to be enforced by the constrained fixation of the nitrile unit within the highly organized coordination pocket of the bimetallic framework. In contrast, the bifunctional 2-hydroxybenzonitrile is accommodated by the distinct binding of the nitrile and phenolate functions to the different metal centers in 8, which confirms that the simultaneous binding of both an OR-function and an end-on bound nitrile is indeed feasible within the active site pocket. Such a situation is reminiscent of the bimetallic effect that has been assumed to enable the cooperative hydration of nitriles at the dinickel(II) site of 1. Complexes 4·(ClO4)2, 5·(ClO4)2, 6·(ClO4)3, 7·(ClO4)(BPh4), and 8·(ClO4)2 have been characterized structurally by X-ray crystallography.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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