Darstellung und Kristallstrukturen einiger intramolekularer Donator‐Akzeptor‐Komplexe mit der Phosphorylgruppe als Donator

Abstract

Preparation and Structures of Some Intramolecular Donor-Acceptor Complexes with the Phosphoryl Group as DonorThe reaction of [2,2-diphenyl-l-(trimethylsiloxy)ethenyl]-F3B . OEtz led to the intramolecular donor-acceptor-complex dimethylphosphane oxide (1) with PF5 yields 2, involving 3 with a tetracoordinated boron atom. The complex 4 with hexacoordinated phosphorus, by cleavage of the Si-0 bond penta-(or hexa)coordinated tin was prepared by reaction of 1 and elimination of (CH3)3SiF. The same compound was formed with tin(1V) chloride with elimination of (CH&SiCl. X-ray in the reaction of 1 with RPF4 (R = dimethylamino, morphol-structure analyses of 2 and 3 confirm the donor-acceptor inino) by cleavage of the P-N bond and elimination of the cor-teraction between the oxygen atom of the P=O group and the responding silylated amine, R,NSiMe3. [2,2-Di-phenyl-I -(trimethylsiloxy)ethenyl]dimethylphosphanoxidP1 (1) enthalt rnit der Trimethylsilyl-Gruppe eine gute Abgangsgruppe sowie die Donator-Gruppierung P=O. Bedingt durch die 1,CStellung der Sauerstoffatome sollte die Bildung von intramolekularen Donator-Akzeptor-Komplexen mit einem funfgliedrigen Ringsystem bevorzugt sein.Im folgenden wird die Darstellung von Donator-Akzeptor-Komplexen durch Si-0-Bindungsspaltung in 1 mittels Fluorphosphoranen, Bortrifluorid-Ether und Zinntetrachlorid beschrieben. Die 'H-, 19F-und 31P-NMR-Spektren des jeweils erhaltenen Produktes waren jedoch rnit denen von Verbindung 2 identisch. Diese ungewohnliche Spaltung einer P-N-Bindung in einem Aminotetrafluorphosphoran durch eine trimethylsilylierte Verbindung wurde erst einmal beobachtet[lol. Da die Lewis-Aciditat von ROPF4 vermutlich groBer Ergebnisse und Diskussion

Neutral Six-Coordinate Phosphorus

“…93 The X-ray crystal structure of 35 ( Figure 20) show clearly the interaction of the octahedral PF 4 center with the PdO group. Significant delocalization may be inferred from the small difference between the P-O and formal P f O bond distances [1.685(2) and 1.732 (2) Å, respectively].…”

“…Reactions of RPF 4 (where R ) F, dimethylamino, or morpholino) with [2,2-diphenyl-1-(trimethylsiloxy)ethenyl]dimethylphosphane oxide yielded compounds with an unusual PdOfP bond 35 (eq 31). 93 The X-ray crystal structure of 35 (Figure 20) show clearly the interaction of the octahedral PF 4 center with the PdO group. Significant delocalization may be inferred from the small difference between the P-O and formal P f O bond distances [1.685(2) and 1.732 (2) Å, respectively].…”

“…Reactions of RPF 4 (where R = F, dimethylamino, or morpholino) with [2,2-diphenyl-1-(trimethylsiloxy)ethenyl]dimethylphosphane oxide yielded compounds with an unusual PO→P bond 35 (eq 31) . The X-ray crystal structure of 35 (Figure ) show clearly the interaction of the octahedral PF 4 center with the PO group.…”

“…Significant delocalization may be inferred from the small difference between the P−O and formal P → O bond distances [1.685(2) and 1.732 (2) Å, respectively].

20 X-ray crystal structure of 35 , redrawn from coordinates retrieved from the Cambridge database. Reproduced with permission of the original authors and the journal.

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“…X-ray crystal structure of 35 , redrawn from coordinates retrieved from the Cambridge database. Reproduced with permission of the original authors and the journal.…”