88657-64-1Relevant academic research and scientific papers
Synthesis, reactivity, and X-ray crystal structure of an anionic, mixed-metal ketenylidene cluster: [PPN][Fe2Co(CO)9(CCO)]
Ching, Stanton,Holt, Elizabeth M.,Kolis, Joseph W.,Shriver, Duward F.
, p. 892 - 898 (2008/10/08)
The anionic mixed-metal ketenylidene cluster [PPN][Fe2Co(CO)9(CCO)] (1) can be prepared in high yield by a facile metal substitution reaction between [PPN]2[Fe3(CO)9(CCO)] and Co2(CO)8 under a CO atmosphere. This cluster is structurally similar to [Fe3(CO)9(CCO)]2-, but its reactivity more closely resembles that of the cationic cluster [Co3(CO)9(CCO)]+. Compound 1 undergoes protonation at the α-carbon atom to give Fe2Co(CO)10(CH) but is inert to electrophilic attack by carbocationic reagents. Nucleophilic reagents such as LiCH3, NaOCH3, and KBEt3H attack at the β-carbon atom to afford dinegatively charged species [Fe2Co(CO)9(CC(O)R)]2- (R = CH3, OCH3, H). Compound 1 crystallizes in the space group C2/c with a = 27.231 (7) A?, b = 17.670 (6) A?, c = 23.072 (10) A?, β = 126.54 (3)°, V = 8919.9 (70) A?3, and Z = 8.
Mixed-metal cluster carbides and a mixed-metal ketenylidene with nucleophilic carbide sites
Kolis, Joseph W.,Holt, Elizabeth M.,Hriljac, Joseph A.,Shriver, Duward F.
, p. 496 - 498 (2008/10/08)
The nucleophilic ketenylidene [Fe3(CO)9-(CCO)]2- (III) serves as a convenient mixed-metal carbide precursor. Compound III reacts readily with labile metal carbonyl fragments such as M(CO)3(NCCH3)3 (M = Cr, W) to generate the new clusters [Fe3MC(CO)13]2- which contain a nucleophilic carbide ligand similar to that in [Fe4C(CO)12]2-. By contrast, treatment of III with Co2(CO)8 leads to replacement of one iron vertex, generating a new monoanionic heterometallic ketenylidene [Fe2Co(CO)9(CCO)]- which is less reactive but otherwise chemically similar to III. X-ray cristallographic analysis shows the CCO tilt to be considerably less than in the [Fe3(CO)9(CCO)]2- species.
