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Expt6Ref1

Ahmad, N.; Levison, J. J.; Robinson, S. D.; Uttley, M. F.


Inorg Synth. 1974, 15, 45-53.

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C39H5003P2Ru:C. 66.0: 51, 4.26; P, 8.73. Found: C, 66.30, 66.0:


H. 4 48, 4.2 : P. 8.87.

I
The complex is moderately soluble in benzene, chloroform, and
dichloromet hane.

Tricarbonylbis(triphenyIphosphine)ruthenium(O) was first prepared by reducing RuCl,(CO), [P(C,H,),],


with zinc dust in
dimethylformamide at 100" under a carbon monoxide pressure
of 4 atmospheres for 24 hours.7 It has subsequently been prepared
by treating [Ru(CO), (P(C,H,), 11, with excess triphenylphosphine
in methyl ethyl ketone solution at 130-140' under a n atmosphere
of carbon m ~ n o x i d e ,and
~ by an autoclave reaction of Ru(CO),
with triphenylphosphine in tetrahydrofuran at 13Q" under a nitrogen
atmosphere.' Passage of carbon monoxide through a mct hanolic
suspension of RuH IOCOCH,) [P(C,FT,),], For ca. 12 hours also
affords tricarbonylbis(ariphe~y1phosphine)ruthenimO).' O

Solutions oh0.39 g. (1.5 rnrnoles) of hydrated ruthenium tsichloride


in 30 ml. of cool 2-mcthoxyethanol, hot aqueous formaldehyde
(30 ml..40:/, w!v). and 0.6 g. of potassium hydroxide in 30 ml. of
hot 2-meahoxyet hanol arc added rapidly and successively to a
well-stirred, boiling solution of 2.37 g. (9 rnrnoles) of triphenylphosphine in 40 m3,of 2-rnethoxyethanol. T h e reaction solution is
stirred and heated under reflux for E hour and then cooled to room
temperature. The resultant yellow microcrystalIine precipitate is
washed with ethanol. water, ethanol, and n-hexane and dried in
cacun. Yield 0.95 g. (89 ?/; based on RuCI, - 3 H 2 0 ) . Anal. Calcd, for

Tricarbonylbis(triphen~1phosphinejrutheiitm)forms pale yetlow microcrystals which melt a t 170-173' in air and at 262-266"
in a capilIary sealed under nitrogen. The infrared spectrum shows
a single very strong band at 1900 cm.-' attributable to v ( C 0 ) .
The complex is moderately soluble in benzene and dichlorornethane.

Trichloroni trosylbis(tripheny1phosphine)ruteium(11) was originally prepared by heating a mixture of [RuCl,(NO)], and triphenylphosphine in ethanol for 5-10 minutes. ' ' It has subsequently
been prepared by treating the complexes RuCl(COj(N0)[P(C,M,),]," or RUCI(NO)[P(C~H~)~]~~~
with chlorine. The procedure
described below is based o n ruthenium trichlotide and eliminates
the need to use preformed ruthenium nitrosy1 derivatives.

Solutions o f 0.39 g. (1.5 mmoles) of hydrated ruthenium ~richlorlde


in 30 ml. of ethanol and of 0.63 g, of N-met hyI-N-nitroso-p-toluenesulfonamide in 30 ml. of ethanol are added in quick succession to
a vigorously stirred, boiling solution of 2.37 g. (9 rnmoles) of triphenylphosphine in 90 mF.of ethanol. The mixture is refluxed for
5 minutes and then cooled to room temperature. The green platelets
deposited are f ltercd, washed with ethanol. water. ethanol, and
n-hexane and are dricd in vacuo. The green, impure complex is
extracted with boiling dichloromeahane ( 5 x tQ0 ml.). The extract
is filtered. evaporated to small volume, and then allowed to crystallize at 0'.The crystals are washed with n-hexane. Yield is 0.92 g.
(80% based on RuCI, .3H,O). Anal. Calcd, for C,,H,,C~,NOP,Ru :