The addition of isonitriles to [{M(CO)₂(η-C₅H₅)}₂](M = Mo or W). Syntheses and properties of [M₂(µ-η²-CNR)(CO)₄(η-C₅H₅)₂](M = Mo or W, R = Me or Bu^t) and [{Mo(CNR)(CO)₂(η-C₅H₅)}₂](R = Me or Bu^t). X-Ray crystal structures of [Mo₂(µ-η²-CNBu^t)(CO)₄(η-C₅H₅)₂] an

Abstract

The Addition of Isonitriles to [{M(C0),(q-C5H5)),] ( M = M o or W). Syntheses and Properties of [M,(p-q2-CNR)(CO),(q-C5H5)J ( M = M o or W, R = M e or But) and [{Mo(CNR)(CO),(q-C,H,)),] (R = M e or But). %Ray Crystal Structures of [Mo,(p-q2-CNBut)( CO),(YJ-C,H,),] and [{Mo( CN But)(CO),(q-CsH,)),] t

Substitution and Hydrogenation Reactions on Rhodium(I)−Ethylene Complexes of the Hydrotris(pyrazolyl)borate Ligands Tp‘ (Tp‘ = Tp, TpMe2)

“…The IR spectrum of binuclear 7a shows a very broad and intense band centered at ca. 1735 cm -1 , i.e., in the region expected for μ 2 -CNR functionalities. − Also worth mentioning is a medium-intensity ν(B−H) stretching vibration at 2480 cm -1 . While in comparison with Tp Me2 compounds there are insufficient data available on ν(B−H) for complexes of the unsubstituted Tp ligand, in the structurally characterized [(κ 3 -Tp)Ru(CO) 2 ] 2 this band appears at 2485 cm -1 .…”

Reactions of Cyclohexyl Isocyanide with η5‐Substituted Cyclo‐pentadienyl MoMo Triply Bonded Complexes. Crystal Structure of [Mo(CO)2(η5‐C5H4CO2CH3)]2(μ‐η2‐CNC6H11)

“…These values imply that the isocyanide ligands of 1a, 1b are bridged to the Mo-Mo single bond in a µ-η 2 -mode and those ligands in 2a, 2b are terminally coordinated to their Mo atoms. 11,12 In the mass spectra of 2a and 2b, the [M＋Na] ＋ peaks appeared at 760 and 792, respectively, and their fragment ion peaks corresponding to ＋ , [M-CO-CNC 6 H 11 ] ＋ were also found at the correct positions.…”

“…In accordance with this type of structures, the ν (N≡C) values of the coordinated isocyanide appear in the range 1900-2125 cm -1 . However, in the case with a smaller steric hindrance situation, the isocyanide favors as a bridging ligand (Figure 1b and 1c), in which the C≡N bond lengths are longer and the ∠Mo1-C-N and ∠C-N-R are smaller than those in the above mentioned terminally coordinated complexes shown in Figure 1a, such as in complexes Mo 2 (CO) 4 (C 5 Me 5 ) 2 (CF 3 NC), 19 Mo 2 (CO) 4 -(C 5 Me 5 ) 2 (CF 3 CH 2 NC) 20 ( Figure 1b), and in complexes Mo 2 (CO) 4 (C 5 H 5 ) 2 (PhNC), 11,21 Mo 2 (CO) 4 (C 5 Me 5 ) 2 -(CH 3 NC), 22 Mo 2 (CO) 4 (C 5 H 5 ) 2 (t-BuNC), 12 Mo 2 (CO) 3 -(C 5 H 5 ) 2 (dppm)(t-BuNC), 23 and Mo 2 (CO) 2 (C 5 H 5 ) 2 (NPh)-(PhNC) (Figure 1c). 24 In addition, the ν (N≡C) values in these complexes are in the range 1600-1750 cm -1 .…”

“…In a Mo-Mo isocyanide complex with more steric hindrance (Figure 1a), the isocyanide ligand used to bond to a Mo atom as a terminal coordination manner, such as in complexes Mo 2 (CO) 4 (Cp) 2 (t-BuNC) 2 , 12 HMo 2 (CO) 7 (NO)(Cy 3 P)-(n-PrNC) 2 (Cy＝c-C 6 H 11 ), 14 HMo 2 (CO) 6 (NO)(µ-dppe)-(n-PrNC), 15 18 In this type of complexes, the ∠Mo 1 -C-N and the ∠C-N-R are close to 180º and the C≡N bond lengths are about 1.15 Å. In accordance with this type of structures, the ν (N≡C) values of the coordinated isocyanide appear in the range 1900-2125 cm -1 .…”

Synthesis and structural characterization of sulfur rich iron (II) carbonyl dimers: Facile reversible reaction with carbon monoxide

“…The formation of the [CpMo(CO) 2 ] 2 dimer in refluxing xylene was shown to occur via odd-electron intermediates arising from the homolysis of the Mo-Mo bond in the Cp 2 Mo 2 (CO) 6 precursor. Soft nucleophiles add to the metalmetal triple bond in this dimer complex, but the reverse reaction with CO to afford [CpMo(CO) 3 ] 2 was not observed [20]. Facile reaction of CO with the Fe@Fe double bond is observed in complex 3, with regeneration of complex 2 observed in minutes when complex 3 is placed under 1 atm of CO (Scheme 4).…”