114184-70-2Relevant academic research and scientific papers
Syntheses and reactions of η5-(dimethylboryl)cyclopentadienyl cobalt and rhodium derivatives. Site-specific binding of unsaturated amines
Klang, Jeffrey A.,Collum, David B.
, p. 1532 - 1537 (2008/10/08)
Syntheses and reactions of (η5-(py·Me2B)C5H4]ML 2 complexes (M = Rh or Co; py = pyridine; C5H4 = η5-cyclopentadienyl) are described. Treatment of [(CO)2RhCl]2 with C5H5(BMe2·py) or (Me3Si)C5H4-(BMe2·py) affords [η5-(py·Me2B)C5H 4]Rh(CO)2 (2) in 24 and 60% yields, respectively. Reaction of (py·BMe2)C5H5 with Co2(CO)8 provides [η5-(py·Me2B)C5H 4]Co(CO)2 (4) in 40% yield. Substitution of 2 with triphenylphosphine affords [η5-(py·Me2B)C5H 4]Rh(CO)(PPh3). Complex 4 is converted sequentially to [η5-(py·Me2B)C5H 4]Co(CO)I2 and [η5-(py·Me2B)C5H4]Co(PPh 3)I2 in high yield. Pyridine exchanges at the boron centers of both 2 and 4 are rapid on NMR time scales at ambient temperatures. The cooperative binding properties of the transition-metal and boron centers are described in the context of chelations of dimethylallylamine (Me2NCH2CH=CH2) to form [η5-(Me2B)C5H4]Co(η 3-Me2NCH2CH=CH2)(CO) and [η5-(Me2B)C5H4]Co(η 3-Me2NCH2CH=CH2)(PPh3) (9). The corresponding rhodium chelates cannot be prepared. Chelate 9 undergoes a photochemically mediated reaction at elevated temperatures with diphenylacetylene to afford a chelated butadiene complex, [η5-(Me2B)C5H4]Co[η 5-R2NCH2CH=CHC-(Ph)=C(Ph)H].
