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• W1556795587 abstract "Abstract The reaction between [Li(dme)AsH 2 ] and (ClSi i Pr 2 ) 2 O gives a mixture of two products: the primary diarsanyldisiloxan (H 2 AsSi i Pr 2 ) 2 O ( 5 ) and the cyclic diarsanylsiloxane (HAsSi i Pr 2 ) 2 O ( 6 ). Through metallation of the mixture, the deprotonated species of both compounds could be obtained and isolated. Further reactions between the two metallated cyclic diarsanylsiloxanes (compounds 9 and 10 ) and (ClSi i Pr 2 ) 2 O both lead to the bicyclic compound As 2 [( i Pr 2 Si) 2 O] 2 ( 11 ). Subsequent oxidative coupling of 9 or 10 with C 2 H 4 Br 2 as reagent leads to intermolecular As–As bond formation, yielding the quite remarkable compound As 6 [( i Pr 2 Si) 2 O] 3 ( 12 ), which features two siloxane‐bridged As 3 rings. Compounds 5 – 12 were characterized by NMR, elemental analysis and X‐ray crystallography. Quantum chemical calculations were carried out to investigate the formation of the different products when arsenic (compound 12 ) is substituted by phosphorus (compound 4 ) in the final oxidation reaction of the cyclic compounds (HESi i Pr 2 ) 2 O. The calculations suggest a reaction path leading to 4 that is in agreement with experimental observations. The theoretical data also provide information that explains the experimental finding that two different products for E = P and E = As are formed under the same oxidative reaction conditions." @default.
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• W1556795587 date "2015-06-22" @default.
• W1556795587 modified "2023-10-12" @default.
• W1556795587 title "Stepwise Synthesis of Siloxane‐Substituted Oligoarsanes and Structural Investigation of Alkaline Earth Metal Derivatives" @default.
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• W1556795587 doi "https://doi.org/10.1002/ejic.201500279" @default.
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