Reaktionen an trans‐Difulminatobis(triphenylphosphin)platin(II)

Abstract

Das thermisch sehr stabile (Ph3P)2Pt(CN0)2 (1) la& sich katalytisch in Gegenwart von organischen Carbonylverbindungen unter milden Bedingungen zur Isocyanatoverbindung (Ph,P)2Pt(NC0)2 isomerisieren. 1 liefert mit organischen Thiocarbonylverbindungen (Ph3P)2Pt(NCS)2. M it Phosphinen wird 1 zur entsprechenden Cyanoverbindung trans-(Ph3P)2Pt(CN)2 reduziert. ober die gefahrlose Darstellung verschiedener gemischter Ful- Reactions of trans-Difulminatobis(triphenylphosphine)platinum(II) 1)The thermally very stable fulminato complex (Ph3P)2Pt(CN0)2 (1) rearranges under mild conditions to the isomeric isocyanato complex (Ph,P)rPt(NCO)z in the presence of organic carbonyl compounds which act as catalysts. (Ph3P) Im Vergleich zu den bisher bekannten Fulminatokomplexen2) ist 1 wegen der einfachen und gefahrlosen Darstellung aus Pt(PPh3)4 und Nitromethan 1) und aufgrund seiner ungewohnlich grol3en thermischen Stabilitat zum Studium der Chemie des koordinierten Fulminatoliganden besonders geeignet.

The First Chemical Achievements and Publications by Justus von Liebig (1803−1873) on Metal Fulminates and Some Further Developments in Metal Fulminates and Related Areas of Chemistry

“…The isomerisation of CNO to NCO was also observed during attempts to stabilise the isofulminic acid or fulminic acid ether complexes (MϪCϵNϪOH or MϪCϵNϪOR) by reaction of [(Ph 3 P) 2 Pt(CNO) 2 ] with acetic acid or Et 3 OBF 4 , [79] [80] in a similar manner to the formation of hydrogen isocyanide by protonation of cyano complexes. [83] Until now isofulminic acid (HONC) could not be detected, even not by the elegant and thorough studies of Maier and co-workers.…”

“…acetone, benzaldehyde) at much lower temperatures. [80] This can be explained by a Huisgen [2ϩ3] cycloaddition of the carbonyl group to the fulminato ligand, to give an (unstable) dioxazolone, similar to nitrile oxides. [22,31,86] 4 AsCNO, from which several (fulminato)metal complexes could be safely prepared.…”

“…[16] Like nitrile oxides, [22] the metal-coordinated fulminate ion can also be deoxygenated with phosphanes; for example, the could be detected by its IR spectrum. [80] The deoxygenation of the fulminato ligand at the metal atom is chemical proof that the fulminate ion is bonded to the metal atom through the carbon atom. [16,18,64a] Isomerisation MϪCϵNϪO Ǟ MϪNϭCϭO Thermal isomerisation of fulminate (at temperatures above 200°C) to the much more stable [81] isocyanate has been observed for several complexes.…”

Azide Chemistry – An Inorganic Perspective, Part II[‡] [3+2]‐Cycloaddition Reactions of Metal Azides and Related Systems

“…[24,88,[563][564][565][566][567][568][569][570][571][572][573][574] On that score, however, the metallo nitrile ylides resemble more closely organic nitrile oxides or nitrile imines rather than alkyl-or aryl-substituted nitrile ylides which conversely show the HOMO with the largest coefficient at the divalent carbon atom. [575] With the exception of compounds 120b which are stable substances due to the presence of the carbanion-stabilizing phosphonio substituent, [569] all other studied metallo nitrile ylides and metallo nitrile imines just like their organic models only exist as short-lived intermediates, generated and reacted 'in situ' (see below).…”

“…Similarly, the isothiocyanato complex [Pt(NCS) 2 (PPh 3 ) 2 ] was formed from the fulminate and thiobenzophenone. [566] Conceivably, these reactions proceed via [2+3]-cycloadditions between the carbonyl (thiocarbonyl) group and the fulminato ligand, but the resulting metallated heterocycle is unstable and decomposes with elimination of a carbonyl compound containing the fulminato oxygen atom (Equation (41)). …”