Metallorganische Lewis‐Säuren, XXXI Reaktionen von Pentacarbonyl(tetrafluoroborato)rhenium mit neutralen und anionischen organischen Cyanverbindungen

Abstract

An das 16-Elektronen-System [Re(CO)J + [z. B. als (0C)?ReFBF3] lassen sich zahlreiche ,,harte" und ,,weiche" Nucleophile addieren". Die metallorganische Lewis-Saure Re(CO):, die bei den stets unter sehr milden Bedingungen ablaufenden Reaktionen intakt bleibt und im IR-Spektrum aufgrund des typischen CO-Musters leicht verfolgt werden kann, erscheint besonders geeignet, um als Sonde das Verhalten verschiedenartiger -auch ambidenter -Liganden zu priifen. Im folgenden berichten wir iiber Reaktionen von Pentacarbonyl(tetrafluoroborato)rhenium mit neutralen und anionischen organischen Cyanverbindungen.

Cooperative Binding of Nitrile Moieties Within a Bimetallic Pocket: Enforcing Side-On π-Interaction With a High-Spin Nickel(II) Site

“…[13] The same is also valid for nitriles bound in an η 2 -or a µ-η 1 ,η 2 (σ,π)-mode to other transition metals. [15] Cnge itself has repeatedly been used as a ligand towards transition metal ions, [16][17][18][19][20] in particular in copper chemistry, [18][19][20] and has hitherto been shown to coordinate either in a monodentate form (nitrile N-donor, C, Scheme 6) or as a bidentate bridging ligand through Scheme 6. Common binding modes of cnge both the nitrile and imino-N atoms (D, Scheme 6), but not through the nitrile-N and a terminal amido-N as is observed in 5 for the first time.…”

Synthesis of Heavy Dicyanamide Homologues from Air‐Stable Precursors

“…There is precedent for such differences in the few characterized DCP‐metal complexes that have been reported . For example, though (DCA)Re(CO) 5 features coordination from the DCA nitrile groups, the homologous DCP complex likely binds to rhenium through the central atom, as evidenced by the significant deshielding of the 31 P NMR chemical shift relative to [Na([18]crown‐6)][DCP] …”

“…There is precedentf or such differences in the few characterized DCP-metal complexes that have been reported. [53] For example,t hough (DCA)Re(CO) 5 features coordination from the DCA nitrile groups, [54] the homologous DCP complexl ikely binds to rheniumt hrough the central atom, as evidenced by the significant deshielding of the 31 PNMR chemical shift relative to [Na( [18]crown-6)][DCP]. [55] In conclusion, am ore safe and efficient synthetic protocol for the generationo fd icyanophosphidea nionsb yP + transfer from at riphosphenium salt, [dppeP][BPh 4 ]i sr eported.…”

Pseudohalogeno‐Metallverbindungen. LXXV. Pentacarbonylrhenium‐und Triphenylphosphangold‐Komplexe mit Pseudohalogeniden: (OC)5ReX, Ph3PAuX (X = ONC(CN)2, o‐MeC6H4SO2C(CN)2,o‐MeC6H4SO2NCN, Ph2(S)PNCN)

“…[5 -7]. Durch Röntgenstrukturanalyse wurde die Koordination von Tricyanmethanid und Dicyanamid über ein Cyanid-N-Atom bewiesen [6]. Ebenso ist eine Reihe von Komplexen Ph 3 PAuX mit Monoanionen be kannt [8].…”

“…: C 33,03, Η 1,29, Ν 5,13, S 5,87; gef. : C 32,16, Η 1,31, Ν 5,02, S 6 2,136,9,131,8,131,5,127,6,125,3 (Aromat),122,6 (NCN),20,2 (CH 3 …”