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The alkyl radical products of β-scission of a cyclic tetraalkoxyphosphoranyl radical are independent of its source.  相似文献   

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Studies on the Coordinative Behaviour of Potentially Four and Fivedentate Bis(salicylidene amino)-Ligands with Ions of the 3d-Elements. Fourdentate bis(salicylidene amino)-ligands (?ONΦCH2ΦNO? and ?ONΦOΦNO?, meaning of the abbreviations see text) with the centres of donor atoms connected by rigid, bifunctional residues, form polymeric complexes MeII(ONΦCH2ΦNO) and MeII(ONΦOΦNO) with cobalt(II), nickel(II), and copper(II). Among the cobalt(II) chelates the structure is uniformly tetrahedral, but the nickel(II) and copper(II) complexes contain square planar central atoms and such with a higher coordination number side by side. The potential fivedentate ligands ON3PPh3NO?, ?ON2O2NO?, and ?ON2S2NO? differ as to their coordinative behaviour. The coordination number of the complexes Ni(ON3PPh3NO) and Co(ON3PPh3NO) is five. On the other hand the compounds Co(ON2S2NO) and Co(ON2O2NO) are tetrahedral. No coordination of the ether or sulfide group is observed. Ni(ON2O2NO) has an octahedral structure which is produced by coordination polymerisation and possibly by coordination of the ether group. The new complexes are compared with the transition metal complexes of simple salicylaldimines.  相似文献   

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Zusammenfassung Die Ni4+ und Ni3+ als Zentralion enthaltenden Komplexe [Ni(C7H7N2O)4] und [Ni(C3H6NO3)3] wurden hergestellt und analytisch und magnetometrisch untersucht. Das Tetrabenzamidoximatonickel(IV) ist diamagnetisch und absorbiert bei =490 nm mit einem molaren Extinktionskoeffizienten =3000. Das Triserinonickel(III) ist paramagnetisch mit eff = 1.71 ± 0.03 [ B ] und absorbiert bei =536 nm mit =1300.
Complexes of tri- and Tetravalent Nickel with nitrogen ligands
The complexes [Ni(C7H7N2O)4] (with benzamidoxime) and [Ni(C3H6NO3)3] (with serine) containing Ni4+ and Ni3+, resp., as central ions were synthesized and studied analytically and magnetometrically. The tetrabenzamidoximatonickel(IV) is diamagnetic and absorbs at =490 nm with a molar extinction coefficient =3000. The triserinonickel(III) is paramagnetic with eff = 1.71 ± 0.03 [ B ] and absorbs at =536 nm with =1300.
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Reaction of Trimethylsilylethers of Unsaturated Alcohols with Schwartz Reagent – Stabilisation of Cyclic Zirconiumorganic Compounds by the Moiety Cp2ZrH2 Besides the normal product of hydrozirconation the reaction of allyltrimethylsilylethers CH2? CHC(R1R2)OSi(CH3)3 ( I : R1 = R2 = H, VIII : R1 = R2 = CH3, X : R1 = H, R2 = CH3) with Cp2Zr(H)Cl yields, as a result of a hydrogenation of the Si? O bond, trimethylsilane and a series of compounds with a Zr? O bond. Depending on the substitution of the α-C atom either dimeric chelates ( III ) or binuclear complexes of the type Cp2Zr(Cl)CH2CH2C(R1R2)OZr(Cl)Cp2 ( IX : R1 = R2 = CH3; XII : R1 = H, R2 = CH3) are formed. Starting with X and excess Cp2Zr(H)Cl the binuclear compound XIII is obtained which may be considered as an adduct of Cp2ZrH2 to the unsaturated chelate Compound XVII with a structure analogous to XIII is synthesized by the reaction of IX with Cp2ZrH2. The 1H-NMR spectrum is in accordance with the existence of cis-trans-isomers of this complex.  相似文献   

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CF3SO2N?SCl2 reagiert mit (CH3)2S[NSi(CH3)3]2, (C4H8)S[NSi(CH3)3]2 oder (C5H10)S[NSi(CH3)3]2 unter Trimethylchlorsilanabspaltung zu den achtgliedrigen S4N4-Derivaten S4N4(NSO2CF3)2(CH3)4 3 , S4N4(NSO2CF3)2(C4H8)2 4a und S4N4(NSO2CF3)2(C5H1 0)2 4b . In den achtgliedrigen SN-Ringen haben die Schwefelatome die Koordinationszahl 3 und 4. Die Röntgenstrukturanalyse von 4a ergab eine Sessel-Konformation. 4a kristallisiert orthorhombisch in der Raumgruppe Pna21 mit a = 17,641(4), b = 6,406(2), c = 19,130(4) Å, dx = 1,815 g cm?3 und Z = 4. Die mittleren S? N-Abstände betragen an den vierfach koordinierten Schwefelatomen 1,597 Å und an den Schwefelatomen mit der Koordinationszahl 3 1,650 Å. CF3SO2N? SCl2 reagiert mit trimethylzinnhaltigen S? N-Verbindungen zum bekannten CF3SO2N[Sn(CH3)3]S(CH3)NSO2CF3 und Dimethylzinndichlorid. Synthesis and X-Ray Structure Analysis of S4N4-Derivatives with Threefold and Fourfold Coordinated Sulfur Atoms CF3SO2N?SCl2 reacts with (CH3)2S[NSi(CH3)3]2, (C4H8)S[NSi(CH3)3]2 or (C5H10S[NSi(CH3)2]2 under elimination of (CH3)3SiCl to yield the eight-membered S4N4 derivatives S4N4?NSO2CF3)2(CH3)4, 3 , S4N4(NSO2CF3)2(C4H8)2 4a und S4N4(NSO2CF3)2(C5H1 0)2 4b . In the eight-membered SN-rings the sulfur atoms have the coordination number 3 and 4. The X-ray structure analysis of 4a revealed a chair conformation. 4a crystallizes in the orthorhombic space group Pna21 with a = 17.641(4), b = 6.406(2), c = 19.130(4) Å, dx = 1.815 g cm?3, and Z = 4. The average S? N distance was found to be 1.597 Å at fourfold coordinated sulfur atoms and 1.650 Å at sulfur with coordination number 3. CF3SO2N=SCl2 reacts with trimethyl tin-containing S? N compounds to the known CF3SO2N[Sn(CH3)3]S(CH3)NSO2CF3 and dimethyl tin dichloride.  相似文献   

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