[3+2] Cycloadditions of Metallo Nitrile Ylides and Metallo Nitrile Imines with Metal Carbonyl, Thiocarbonyl, and Isocyanide Complexes: Heterodimetallic Systems with Bridging Heterocycles [1] 

Abstract

The reactions of [Re(CO)6]+, [FeCp(CO)2CS]+ and [FeCp(CNPh)3]+ with the metallo nitrile ylides [M–{C+=N–C–(H)CO2Et}(CO)5]– (M = Cr, W) and the chromio nitrile imine [Cr–{C+=N–N–H}(CO)5]– (generated by mono‐α‐deprotonation of the parent isocyanide complexes) to give neutral 5‐metallated 1,3‐oxazolin‐ (1), 1,3‐thiazolin‐ (2), imidazolin‐ (3, 4), 1,3,4‐oxdiazolin‐ (5), 1,3,4‐thiadiazolin‐ (6) and 1,3,4‐triazolin‐2‐ylidene (8) chromium and tungsten complexes represent the first all‐organometallic versions of Huisgen’s 1,3‐dipolar cycloadditions. The formation of 6 and 8 is accompanied by partial decomposition to (OC)5Cr–C≡N–FeCpL2 {L = CO (7), CNPh (9)}. The structures of 4a and 5 have been characterized by X‐ray diffraction.

N-heterocyclic carbene complexes of Group 6 metals

“…In Cr-36a, the Cr-C carbene bond is 2.157(9) Å and Re-C is 2.135(9) Å[125]. 23 M(0) in dinuclear or heteronuclear-NHC complexes prepared from a [3+2] cycloaddition reaction[125] Cyclisation reactions can be also used to synthesize dinuclear M(0)NHC Cr-37(a-c), W-41(a,b)complexes from a four-component condensation of anion cyano complexes [M(CN)(CO) 5 ]¯ (M = Cr, W) with isocyanides, aldehydes, and diamine salts. Cr-38 is formed when an aldehyde is replaced by a dialdehyde (Scheme 2.15)[90].…”

A Simple and Direct Method for the Palladium‐Catalyzed Oxidative Coupling of Unactivated Allylarenes with Classic Arenes

“…Table 8) representing a first all‐organometallic version of Huisgen's 1, 3‐dipolar cycloadditions . With carbonyl, thiocarbonyl and isocyanide metal complexes, neutral 5‐metallated 1, 3‐oxazolin‐, 1, 3‐thiazolin‐, imidazolin‐, 1, 3,4‐oxadiazolin‐, 1, 3,4‐thiadiazolin‐ and 1, 3,4‐triazolin‐2‐ylidene chromium and tungsten complexes ( 134 , 135 ) have been obtained 89 …”

“…sections 1.8. , 3.3 ., 4.1. ), [27 ] as well as some related chemistry with further organometallic 1, 3‐dipoles ( fulminato complexes , metallo nitrile ylides, metallo nitrile imines) or metal‐substituted (isolobal) dipolarophiles from the authors' laboratories and others 88,89. Side issues such as new metal‐promoted or metal‐catalyzed syntheses of the heterocycles in question, their modes of coordination, or the highly topical hydro(solvo)thermal in situ syntheses of novel (“clickable”) mainly tetrazole‐based metallo‐organic hybrid materials (MOFs) will be quoted by way of example (cf., e.g., sections 1.3. , 1.5. , 3.3. , 4.3 .…”

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

“…), [27] as well as some related chemistry with further organometallic 1,3-dipoles (fulminato complexes, metallo nitrile ylides, metallo nitrile imines) or metal-substituted (isolobal) dipolarophiles from the authors' laboratories and others. [88,89] Side issues such as new metal-promoted or metal-catalyzed syntheses of the heterocycles in question, their modes of coordination, or the highly topical hydro(solvo)thermal in situ syntheses of novel ("clickable") mainly tetrazole-based metalloorganic hybrid materials (MOFs) will be quoted by way of example (cf., e.g., sections 1.3., 1.5., 3.3., 4.3.). Several reviews on reactions of azido metal complexes have appeared, the first one in 1973 by Dori and Ziolo, [40] others by Strähle, [90] Kukushkin and Kukushkin, [91] and Drygina and Garnovskii, [92] together with some short surveys from our group.…”