476445-54-2Relevant academic research and scientific papers
Borane B-C bond cleavage by a low-coordinate iron hydride complex and N-N bond cleavage by the hydridoborate product
Yu, Ying,Brennessel, William W.,Holland, Patrick L.
, p. 3217 - 3226 (2008/10/09)
The iron(II) hydride dimers [LRFe(μ-H)2FeL R] (LMe = 2,4-bis(2,6-diisopropylphenylimino)pent-3-yl; LtBu -2,2,6,6-tetramethyl-3,5-bis(2,6-diisopropylphenylimino)hept-4- yl) abstract hydrocarbyl groups from BR′3 (R′ = Et, Ph) to give LRFeR′ and LRFe(μ-H) 2BR′2. Mechanistic studies with R = R′ = Me are consistent with a process in which the hyride dimer opens one Fe-H bond, and subsequent B-H bond formation is concerted with dissociation of an Fe-H unit. Cleavage of boron-carbon bonds is likely to proceed at least in part from transient quaternary borate anions formed through disproportionation of HBEt3-. In a separate bond-breaking reaction, L MeFe(μ-H)2BEt2 reacts with N 2H4 to form a 1:1 adduct, which has been crystallographically characterized. Upon heating, it ejects H2 from the bridging hydrides and cleaves the N-N bond to form the diaminoborate complex LMeFe(μ-NH2)2BEt2. These novel bondbreaking reactions are facilitated by the low coordination number at the iron(II) center.
Three-coordinate, 12-electron organometallic complexes of iron(II) supported by a bulky β-diketiminate ligand: Synthesis and insertion of CO to give square-pyramidal complexes
Smith, Jeremy M.,Lachicotte, Rene J.,Holland, Patrick L.
, p. 4808 - 4814 (2008/10/08)
The preparation of a series of three-coordinate, 12-electron organometallic complexes of iron(II) supported by a bulky β-diketiminate ligand is described. The thermally stable complexes LFeR (R = Et, CH2tBu, iPr) are three-coordinate in both the solid state (single crystal X-ray diffraction) and solution. They react rapidly with CO to form the diamagnetic complexes LFe(CO)2(COR), which have an unusual square-pyramidal geometry. Spectroscopic and crystallographic studies show that the acyl group is in the axial position. As a result, there are two orientations of the acyl group about the Fe-C bond, and the isomeric ratio is dependent on the size of R. The two isomers are in equilibrium in solution at room temperature.
