Dichlorcyclopropenon als stabiler Komplexligand. Die Kristallstruktur von [NbOCl₃·OC₃Cl₂]₄ / Dichlorocyclopropenone as Stable Complex Ligand. The Crystal Structure of [NbOCl₃·OC₃Cl₂]₄

Abstract

<jats:p>The reaction of tetrachlorocyclopropene with NbOCl<jats:sub>3</jats:sub> yields NbCl<jats:sub>5</jats:sub>·OC<jats:sub>3</jats:sub>Cl<jats:sub>2</jats:sub> (1); 1 is also formed by partial hydrolysis of C<jats:sub>3</jats:sub>Cl<jats:sub>3</jats:sub><jats:sup>+</jats:sup>NbCl<jats:sub>6</jats:sub><jats:sup>-</jats:sup> (2), which is prepared from C<jats:sub>3</jats:sub>Cl<jats:sub>4</jats:sub> and NbCl<jats:sub>5</jats:sub>. [NbOCl<jats:sub>3</jats:sub>·OC<jats:sub>3</jats:sub>Cl<jats:sub>2</jats:sub>]<jats:sub>4</jats:sub> (3) was obtained by hydrolysis of 1 in form of pale-yellow, moisture sensitive, non-explosive crystals, and characterized by its IR spectrum and an X-ray crystal structure determination (1871 independent observed reflexions, R = 0.048). Crystal data: space group P1̄. Z = 2. a = 993.7(4), b = 1090.5(5). c = 1097.4(3) pm, α = 69.51(3), β = 70.47(3), γ = 66.51(4)° (at -17 °C). 3 consists of centrosymmetrical tetramers; the four Nb atoms form a square and are linked via almost linear oxo groups with alternating short and long NbO bonds with mean bond lengths of 175 and 208 pm. In trans position of each of the short NbO bonds a dichlorocyclopropenone molecule is attached via its oxygen atom with an NbO distance of 223 pm.</jats:p>

Structural and Functional Evolution of Metallacrowns

“…These metallamacrocycles typically have either a square or rectangular shape, although the polygon can be slightly distorted in many instances. 8-MC-4 complexes with oxygen atom connectivity have been synthesized with Li I , 560 Al III , [561][562][563] Ti IV (Figure 94), [564][565][566][567][568][569][570][571][572][573][574][575][576][577][578][579][580] V IV , 581,582 V V , 583-587 mixed-valent V IV 2 V V 2 , 588,589 Mn II , 590 Mn III , 591,592 mixed-valent Mn II Mn III 3 , 593,594 Fe III , [595][596][597][598][599][600][601] Co II , 590 Ni II , 602,603 Cu I , [604][605][606][607] Cu II , 590,608-619 Zn II , 602,620-625 Ge IV , 626,627 Nb IV , 628 Nb V , [629][630][631]...…”

Cyclopropenylium Cations, Cyclopropenones, and HeteroanaloguesRecent Advances

“…Complex 426 was synthesized by treatment of tetrachlorocyclopropene with NbCl 5 and subsequent partial hydrolysis (eq 227). 390 The structures of compounds 417, 378,379 418, 380 419, 381 420, 381 423 (n ) m ) 2), 386 425 (R ) Bu t ), 389 and 426 390 were determined by X-ray single-crystal analysis. Intramolecular bridging was observed for the crystals of 417 (Figure 21) and 426 (Figure 22).…”

“…Except for 426 , all the complexes were prepared by the reaction of a cyclopropenone and a metal reagent. Complex 426 was synthesized by treatment of tetrachlorocyclopropene with NbCl 5 and subsequent partial hydrolysis (eq 227) …”

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22 ORTEP drawing of complex 426 . [Reprinted with permission from ref . Copyright 1988 Verlag der Zeitschrift für Naturforschung.

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