Metallcarbonyl‐Synthesen, XXI. Einfache Synthese eines präparativ nützlichen Alkoxy(carbonyl)metallats

Low-valent Organorhenium Compounds

“…2 The classic preparative route toward [Re 2 (CO) 1 O 7 ] on a small scale, but requires high CO pressures (36 MPa), temperatures o f 250 °C, and the use of an autoclave lined with a Cu-Ag alloy. 3 Low temperature (150 °C) 4 and relatively low pressure (10 MPa CO) 5 routes toward [Re 2 (CO) 1 0 ] have been reported, but the yields are 80% and 69% respectively.…”

“…The r| 3 -benzyl complex (2), generated from Na[Re(CO) 5 ] and Ph 3 CPF 6 , serves as a useful precursor to rhenium radicals (Equation (1)). Upon heating (2) is converted to the rj 5 -cyclohexadienyl complex (3), which reacts with added phosphine to give the persistent rhenium radical [Re(CO) 3 L 2 ] (L = PCy 3 , PPr' 3 ) (Equation (I)). 15 ' 16 Complex (1) was structurally characterized and found to be a distorted square pyramid.…”

“…64 Crystallographic analysis indicates t h a t the f o u r rc-electrons in the trinuclear core a r e delocalized, resulting in rhenium-rhenium bonds with some double bond c h a r a c t e r (average Re-Re 0.273 0(1) nm). 74 Donor molecules such as CO, PPh 3 , MeCN, a n d H 2 75 The n e u t r a l u n s a t u r a t e d t e t r a n u c l e a r cluster [Re 4 (H) 4 …”

“…108 2 ] is accessible f r o m rhenium atom vapor and Cp*H, albeit in 11% yield. 117 Both of these hydrides are converted to 17-electron rhenocene radicals upon photolysis.…”

Ab initio and DFT study of luminescent cyclometalated N-heterocyclic carbene organogold(III) complexes

“…The singlet NHCs are stabilized by the interaction of the empty p-orbital with the two neighboring nitrogen lone pairs [3]. Earlier work considered NHCs as phosphine analogues [4,5], but the recent observations emphasized some differences in steric and electronic properties and their chemical behavior [6][7][8]. Since these ligands act as excellent strong σ-donors, they can produce stable metal− NHCs with strong metal−carbon bonds [9][10][11].…”