Hydrogenation of acetone and fate of propene in the presence of different homogeneous Ru catalysts^a.

Entry	Catalyst	Substratee	Olefin Selectivityf	Propeneg (%)	Propaneg (%)	Isopropanolh (%)	Acetoneg (%)
0	RuBr3·xH2O + COb	Glycerol	94%	82	5	2	4
1	RuBr3·xH2O	Acetone	/i	2	<1	<1	53
2	[RuCl2(CO)3]2	Acetone	36%	25	44	26	3
3	[RuBr2(CO)3]2	Acetone	30%	17	40	29	8
4	[RuBr2(CO)3]2 + COb	Acetone	52%	25	23	46	4
5	RuBr 3 ·xH 2 O + COb	Acetone	90%	77	8	2	<1
6	RuBr3·xH2O + COb,c	Acetone	82%	72	16	<1	<1
7	RuBr3·xH2O + COb,d	Acetone	93%	40	3	1	50
8	RuBr3·xH2O	Propene	39%	38	59	—	—
9	[RuCl2(CO)3]2	Propene	56%	52	41	—	—
10	[RuBr2(CO)3]2	Propene	63%	62	36	—	—
11	[RuBr2(CO)3]2 + COb	Propene	82%	78	17	—	—
12	RuBr 3 ·xH 2 O + COb	Propene	96%	95	4	—	—
13	RuBr3·xH2O + COb,c	Propene	87%	84	13	—	—
14	RuBr3·xH2O + COb,d	Propene	98%	93	2	—	—

^aReaction conditions unless stated otherwise: 0.01 mmol Ru_cat. (2 mol%), 1.7 mmol Bu₄PBr, 1 mL dodecane, 0.5 mmol tetradecane (IS), 220 °C, 40 bar H₂, 1 h.

^bPretreatment step of RuBr₃ with CO gas (1 bar), 30 min, 40 bar H₂, 180 °C.

^cReaction for 4 h.

^dCO gas (1 bar) present during the reaction.

^eGlycerol: ref. 7: HBr co-catalyst (5 mol%), crude glycerol (0.5 mmol). Acetone (0.5 mmol, 36.7 μL). Propene gas (1 bar).

^fRatio of propene vs. (propene + propane) determined by FT-IR/GC gas analysis.

^gGC yield.

^hGC yield after BSTFA derivatization.

ⁱYield too low to allow reliable selectivity determination.