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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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Formation of derivatives of PQQ and PQQ-Triester for the Detection of PQQ PQQ is an organic redox/cofactor found in a class of enzymes called quinoproteins. It has been reported that materials like milk, egg yolk, vinegar, beer, serum, urine, and biological tissues contain little amounts of PQQ . To facilitate studies on PQQ , a simple detection of PQQ could be extremely useful. For this purpose, we describe in this paper some adducts of PQQ or PQQ -triester with 1,2-diamines, 2,4-dihydroxyaniline, pyrrole, indole as well as an oxidation product of PQQ . UV and fluorimetric detections of these colored products show that this method is relatively sensitive. The reaction of PQQ -triester with (MeO)3P to the phosphole adduct 13 is of great importance: the use of [32P]-labeled trialkyl phosphites will make this reaction an extremely sensitive method to detect PQQ .  相似文献   

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