Organometallics 1985, 4 , 1882-1886
1882
Two New Tetranuclear Ruthenium Complexes: [Ru,(CO),(PPh,)(C2PPh,)], with Two binuclear Units Linked by Two Phosphinoacetylide Bridges and [RU~(CO),~(PP~)(P~C,PP~,)], a Flattened “Butterfly” with a cr-7r-Phenyl(dipheny1phosphino)ethyne and a p4-Phosphinidene Extracted from the Bis(dipheny1phosphino)et hyne Reactant Jean-Claude Daran, Yves Jeannin, and Olof Kristiansson Laboratoire de Chimie des M6faux de Transition, U.A. 4 19, Universitg Pierre et Marie Curie, 75230 Paris Cedex 05, France Received February 7, 1985
Syntheses and single-crystal X-ray diffraction studies of two derivatives isolated from the reaction of bis(dipheny1phosphino)ethyne with dodecacarbonyltriruthenium are reported. Crystal data for compound I, [RU~(CO)~(PP~,)(C~PP~~)]~: tetragonal, space group P41212,a = 23.13 (2) A, c = 13.54 (1)A, R = 0.0581, R, = 0.0496 for 2181 reflections. Crystal data for compound 11, [RU,(CO)~~(PP~)(P~C~PP~,)]: triclinic, space group Pi,a = 12.50 (5) A, b = 13.28 (5) A, c = 21.32 (7) A, a = 137.7 ( 1 ) O , p = 107.1 (2)O, y = 100.1 ( 2 ) O , R = 0.0551, R, = 0.0495 for 3932 reflections. Compound I contains two dinuclear subunits linked by two phosphinoacetylide bridges; each subunit is similar to known u-n-acetylide bimetallic derivatives with a phosphido bridge. Compound I1 is a tetranuclear cluster with a flattened “butterfly” geometry capped on one side by a phenyl(dipheny1phosphino)ethyne a-a-bonded to the four ruthenium atoms with its phosphino group making a three-membered Ru-P-C ring similar to a phosphirene ring and on the other side by a phosphinidene group extracted from the original bis(dipheny1phosphino)ethyne.
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Introduction
and one tetranuclear cluster exhibiting a rare and unexpected extraction of a phosphinidene group from the bis(dipheny1phosphino)ethyne.
As part of our continuing synthetic and structural studies in the area of functionalized alkyne-cluster chemistry, we recently reported an unusual tetranuclear complex Experimental Section of ruthenium obtained from the reaction of [ R U ~ ( C O ) ~ ~ ] Syntheses. Bis(dipheny1phosphino)ethyne [ (C6H5)2PC=Cwith 1-(diethy1amino)propyne that contained two pentaP(C,H,),] (432 mg, 1.1mmol) was dissolved in 30 mL of tetradentate cyclopentadienolato ligands.’ We then became hydrofuran and slowly added to a solution of [ R u ~ ( C O )(700 ~~] interested in another functionalized alkyne, bis(dimg, 1.1mmol) in 80 mL of tetrahydrofuran. The solution was pheny1phosphino)ethyne (dppa). Reactions of monostirred and refluxed for 18 h under dry nitrogen. The mixture phosphinoalkynes RCECPR’~with metal carbonyls were was evaporated and chromatographed on a 40 X 1.5 cm neutral recently re vie wed;,^^ this chemistry is dominated by the alumina column. Mixtures of hexane/benzene were used to elute five orange bands. The two first fractions were evaporated, and cleavage of the P-C(a1kyne) bond and the formation of recrystallizations from hexane yielded three products. (i) Oracetylide-type complexes. Although symmetric phosphiange-yellow crystals of 1:IR v(C0) 2080 (w), 2030 (vs),1960 (sh), noalkynes might offer the possibility for two P-C(a1kyne) 1880 (s) cm-’. Anal. Calcd for R U ~ C ~ ~ H ~ O ~ J ’ ~ : 1950 (vs),1910 (w), bond cleavages, results refer mainly to compounds in which C, 50.55; H, 2.74. Found: C, 50.48; H, 2.94. (ii) Red crystals of P-C bond rupture does not occur. Carty et al. have re11: IR v(C0) 2065 (w), 2030 (vs), 1985 (sh), 1980 (s), 1970 (s), 1842 ported a compound which consists of two [Fe2(CO),(v(vs) cm-’. Anal. Calcd for R u ~ C ~ ~ C,H40.08; ~ ~ H, ~ 1.87. ~ ~ P ~ : C5H5)Junits linked by a dppa molecule4 whereas Cotton Found: C, 40.25; H, 2.0. (iii) Black crystals of I11 IR u(C0) 2050 et al. have isolated tantalum complexes in which the (s), 2010 (vs), 1980 (sh),1960 (sh), 1925 (m) cm-l. Anal. Calcd acetylene is dimerized to give a 1,2,3,4-tetraphosphinofor R u ~ C ~ ~ C, H37.06; ~ ~H,~ 1.60. ~ ~Found: P ~ :C. 37.92; H. 1.85. This last compound is not discussed here.’ but-Zenediyl chain linked to metal atoms through P-C-Ta X-ray Analyses. For both compounds, preliminary unit cell rings.5 More recently, Rudler et al. have reported the dimensions and symmetry information were derived from Laue insertion of this dppa into one of the C-W bonds of a and precession photographs; in the case of compound I, P4,2,2 (palky1idene)tungsten compound, followed by a P-C bond or the enantiomorphous P43212 were deduced from the examirupture.6 nation of hkO and hO1 zero layers and hkl, hk2, h l l , and h21 upper We report here the syntheses and characterization of two layers. The absolute configuration was not determined. Crystals tetranuclear ruthenium complexes: one containing two then were set up on a laboratory-made automatic three-circle dinuclear units linked by two phosphinoacetylide bridges diffractometer. Cell dimensions and orientation matrices were obtained from least-squares refinements of nine reflections for which 9” < 0 < 1 2 O . A takeoff angle of 3 O was used. Crystal data and data collection parameters are listed in Table (1) Daran, J. C.; Jeannin, Y. Organometallics 1984, 3, 1158. ( 2 ) Sappa, E.; Tiripicchio, A.; Braunstein, P. Chem. Reu. 1983,83, 203. I. Intensities of two standard reflections were monitored every ( 3 ) Carty, A. J. Pure A p p l . Chem. 1982, 54, 113. 100 reflections. These showed no appreciable change during the (4) Carty, A. J.;Efraty, A,; Ng, T. W.; Birchall, T. Inorg. Chpm. 1970. data collections. In the absence of attenuation filters on the 9, 1263. (5) Cotton, F. A.; Falvello, L. R.; Najjar, R. C. C)rganometallics 1982. 1 , 1640. (6) Levisalles, J.; Rose-Munch, F.; Rudler, H.: Daran, J . C.; Jeannin, Y. J . Orwnomet. Chem. 1985, 279. 413.
0276-7333/85/2304-1882$01.50/0
( 7 ) Daran, J . C.; Kristiansson, 0.;Jeannin, Y. C. R. Acad. Sei., Ser. 2 1985, 19, 943.
C 1985 American Chemical Society
Organometallics, Vol. 4, No. 10, 1985 1883
Tetranuclear Ruthenium Complexes
Table I. Summary of X-ray Analyses for Complexes I and I1 I A. Crystal Data formula cryst system systematic absences
(Ru,C,,H*oPzO, 1 2
P4,2,2
OOZ,Z = 4n
+
R~~C36H20P7,010
1; hO0,h = 2n
23.13 ( 2 ) 23.13 ( 2 ) 13.54 ( 1 ) 90.0 90.0 90.0 7244 4 1473.2 1.35 8.99
a, A
b, A c, ‘4 0,
I1
deg
P , deg
z mol wt p(calcd), g cm-3 p , cm-’
+
P1
1 12.50 ( 5 ) 13.28 ( 5 ) 21.32 ( 7 ) 137.7 ( 1 ) 107.1 ( 2 ) 100.1 ( 2 ) 1804 2 1078.8 1.99 17.06
B. Data Collection
diffractometer radiatn monochromator scan range, deg scan type scan speed, deg min-’ scan width, deg in e reflctns obsd criterion
F(000)
laboratory-made, automatic three circle diffractometer M o K a ( A = 0.710 69 A )
graphite monochromator set in front of the counter 3 < 28
e -28
< 46
1.25 (1.10 + 0.345 tan 2566 F > 3o(F) 2911.92
C. Refinement of the Structures final no. of variables 173 reflectns used 2181 R = Z I(F0 - FC)I/Z(F~) 0.0581 R, = { X w ( F o - F c ) 2 / ~ w ( F o ) 2 } L ’ z 0.0496 weighting scheme (UI = k / u ( F o ) Z )k, = 1.06 GOF 1.59
diffractbmeter,intensitieswere corrected for counting losses when the counting rate exceeded 7000 counts s-’. No absorption corrections were considered to be necessary (JI = 8.99 cm-’ and crystal dimensions 0.3 X 0.2 x 0.2 mm for I; = 17.06 cm-’ and crystal dimensions 0.25 X 0.2 X 0.1 mm for 11). Computations were performed by using SHELX 76* on a PDP 11l23 computer for the first stages of calculations and on a GOULD CONCEPT 32/87 for the last full-matrix cycles of refinements. Atomic scattering factors for neutral Ru, P, 0, and C were taken from ref d, those for H were taken from Stewart et al.,1° and anomalous dispersion terms for Ru were included.1° In both compounds, the position of the Ru atoms were determined from a Patterson map. All other non-hydrogen atoms were located on subsequent electron density and difference electroh density maps. Phenyl rings were considered as rigid groups and assigned a refineable overall isotropic thermal parameter. Refinements were by full-matrixleast squares including isotropic and then anisotropic temperature factors for nongroup atoms. All refinements began with unit weighta that were replaced in the final rounds of calculations by a weighting scheme of the form w = k / u 2 ( F ) . For the last cycles of refinement, hydrogen atoms were added to the rigid groups (H-C-H = 120O; C-H = 0.95 A). The criteria for a satisfactory completed analysis were that the ratios of the parameter shifts to standard deviations were all less than 0.04 and that there were no significant features in the final difference maps. The main features of the refinements appear in Table I, part C. Final positional parameters and their standard deviations, obtained from the last cycle of least-squares refinement, are presented in Tables I1 and 111. Thermal parameters for nonhydrogen atoms and final values of observed and calculated (8) Computer programs used were Sheldrick’s SHELX 76, Johnson’s ORTEP-z, and locally written routines.
(9) ‘International Tables for X-ray Crystallography”;Kynoch Press: Birmingham, England, 1974; Vol. IV. (10) Stewart, R. F.; Davidson, E.; Simpson, W. J. Chem. Phys. 1968, 42, 3175.
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