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Upstream product

• 87370-05-6 [2,2,2-(PPh₃)2(CO)-nido-2-OsB₅H₉] 
• 1663-45-2 1,2-bis-(diphenylphosphino)ethane 

Relevant academic research and scientific papers

Degradation and modification of metallaboranes. Part 4: Synthesis and characterization of a series of hybrid bimetallaborane clusters of the type [2,2,2-(PPh3)2(CO)-nido-2-OsB4H 7-3-(BH2PPh2)CxHyPPh 2RuCl2(p-cym)]

Reactions between a series bidentate phosphines, with the general formula PPh2(CH2)nPPh2, and the air stable hexaborane(10) analogue [2,2,2-(PPh3)2(CO)-nido-2-OsB 5H9] (1), afford species of the type [{(PPh 3)2(CO)OsB4H7}-3-{BH 2PPh2(CH2)n(PPh2)}] (2) which contain a pendent PPh2 group. In solution 2 can undergo an intramolecular substitution reaction to form the species [{(PPh 3)(CO)OsB4H7}-η2-3,2-{BH 2PPh2(CH2)n(PPh2)}] (4). In spite of this, chemistry at the pendent PPh2 group may be studied and herein are reported the results of reactions of 2 with the organometallic reagent [(p-cym)RuX2]2 (X = Cl, I) to afford hybrid bimetallaborane clusters of the type [2,2,2-(PPh3) 2(CO)-nido-2-OsB4H7-3-(BH2PPh 2)CxHyPPh2RuCl2(p-cym)] (5) The species obtained include [2,2,2-(PPh3)2(CO)-nido- 2-OsB4H7·3-(BH2·dppe·Ru(p- cym)Cl2)] (5a), [2,2,2-(PPh3)2(CO)-nido-2- OsB4H7·3-(BH2·dppp·Ru(p- cym)Cl2)] (5b), [2,2,2-(PPh3)2(CO)-2-nido- OsB4H7·3-(BH2·dpph·Ru(p- cym)Cl2)] (5c), [2,2,2-(PPh3)2(CO)-nido-2- OsB4H7-3-(BH2·dppx·Ru(p-cym) Cl2)] (5d) and [2,2,2-(PPh3)2(CO)-nido-2- OsB4H7-3-(BH2·dppe·Ru(p- cym)I2)] (6). Species 5d was also prepared from the reaction between 1 and the known compound·[dppx·Ru(p-cym)Cl2. Species 5a-5d and 6 were characterized by elemental analysis, high resolution mass spectrometry and NMR spectrometry; the latter affording some novel features for this series of compounds. Structure determination by X-ray diffraction was not successful but a structure of the analogue [BH3·(PPh 2)(CH2)6(PPh2)·Ru(p-cym) Cl2] (7) is reported.

Degradation and Modification of Metallaboranes: Reactions of the Hexaborane(10) Analogue nido-(PPh3)2(CO)OsB5H9 with Phosphines and the Crystal and Molecular Structure of [2,2,2-(PPH3)2(CO)-nido-2-OsB4H7-3-BH2.PPh2.Me]

The reaction between the osmahexaborane [2,2,2-(PPh3)2(CO)-nido-2-OsB5H9] (1) and bases such as PPh3, PPh2Me, and PMe3 in refluxing CH2Cl2 affords unique adducts of the type [2,2,2-(PPh3)2(CO)-nido-2-OsB4H7-3-BH2.PR3] (2) for which spectroscopic data suggest the presence of a pendent boryl group. This was confirmed by a crystal structure determination for the PPh2Me adduct which shows that 2 is a nido-osmapentaborane with a terminal BH2.PPh2Me moiety on a basal boron atom adjacent to the metal. The reaction is reversible in the case of PPh3 and to a lesser extent PPh2Me, but not for PMe3. Heating the PPh3 adduct affords the osmahexaborane 1, liberating PPh3, but degradation to the osmapentaborane [2,2,2-(PPh3)2(CO)-nido-2-OsB4H8] (6) and BH3.PPh3 competes. The tendency to degrade to phosphine.borane increases markedly down the series R3 = Ph3, Ph2Me, and Me3. When the bidentate bases [1,2-(PPh2)2(CH2)2] and [1,3-(PPh2)2(CH2)3] (abbreviated as dppe and dppp, respectively) are used, two major products are observed in each case. One (3a) [2,2,2-(PPh3)2(CO)-nido-2-OsB4H7-3-(BH2.dppe)] (or 3b, BH2.dppp) is analogous to 2 with one end of the bidentate phosphine donor uncoordinated. In the other (4a) [2,2-(PPh3)(CO)-nido-2-OsB4H7-η(2)-3,2-(BH2.dppe)] (or 4b, BH2.dppp), the free end of the bidentate ligand has replaced a PPh3 group on Os. In the reaction of [(PPh2)2(CH2)] (abbreviated as dppm) with 1, only a species analogous to 3 is observed. The species 3b, the one involving dppp, has beenfurther modified at the free phosphine end of the ligand, to form [2,2, 2-(PPh3)2(CO)-nido-2-OsB4H7-3-(BH2.dppp.BH3)] (5).