Naphthyne: Osmium and Ruthenium Cluster Derivatives

William R. Cullen, Steven J. Rettig, and Tu Cai Zheng ... Claudia Babij, C. Scott Browning, David H. Farrar, Igor O. Koshevoy, Ivan S. Podkorytov, Ant...
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Organometallics 1995, 14,1466-1470

1466

Naphthyne: Osmium and Ruthenium Cluster Derivatives William R. Cullen,* Steven J. Rettig, and Tu Cai Zheng Chemistry Department, University of British Columbia, Vancouver, British Columbia, Canada V 6 T 121 Received November 7,1994@ Reaction of the 1-naphthyl derivatives E(l-C10H7)3(E = P, As)with M3(C0)1z (M = Ru, Os) affords the series of naphthyne complexes M3(CO)sCu-H)zlu3-);l4-(CloH~)2E(CloHs)l (5-8) in moderate to good yield, via double metalation of the unsubstituted aromatic ring. Metalation of the substituted aromatic ring results in one complex, OS~(CO)~C~-H)[(C~OH~)~P(CloHs)]. Cleavage of an As-naphthyl bond affords a low yield of the naphthyne complex R U ~ ( C O ) ~ ~ C ~ - C O ) ~ ~ ~ - A S ( C(ll), ~ ~ Hin~which )]~~~ the - Caryne ~ O Hring ~ ] is at an angle of 75" to the Ru4 plane and acts as a four-electron donor making 11 formally electron deficient. b = 9.688(2) A, c = 33.521(1) A, p = Crystals of 5 are monoclinic, with a = 25.746(1) 108.647(3)",2 = 8, and space group C2/c. Those of 11 are triclinic, with a = 11.433(3) A,b - 14.745(2) A, c = 9.958(1) A, a = 96.81(1)", p = 102.34(2)", y = 78.69(2)", 2 = 2, space group P1. The structures were solved by the Patterson method and were refined by fullmatrix least-squares procedures to R = 0.033 and 0.030 (R, = 0.031 and 0.028) for 5308 and 4933 reflections with I I30(I), respectively.

A,

Introduction The thermolysis of phosphine or arsine derivatives of M3(C0)12 (M = Ru, Os) is a well-established method of preparing aryne derivatives of metal clusters such as the benzyne, ferrocyne, and (benzyne)chromium tricarbony1 derivatives 1-4.1-4 In some cases the derivatives

There are no reports of naphthyne complexes of metal clusters; therefore, it was of interest to establish if these could be prepared by pyrolysis reactions. The present paper describes the successful synthesis of such derivatives via the reaction of tris(1-naphthy1)arsine and -phosphine with M3(CO)12 (M = Ru, Os).

Experimental Section

Fc

1

2

Fc

3

4

are more easily obtained by pyrolyzing M3(C0)12 with the appropriate arsine or phosphine. Abstract published in Advance ACS Abstracts, January 15, 1995. (1)Bennett, M. A,; Schwemlein, H. P. Angew. Chem., Int. Ed. Engl. 1989,28, 1296. For a recent example see: Cullen, W. R.; Rettig, S. J.; Zhang, H. Organometallics 1991,10,2965. (2) (a) Zheng, T. C.; Cullen, W. R.; Rettig, S. J. Organometallics 1994,13,3594. (b) Knox, S. A. R.; Lloyd, B. R.; Morton, D. A. V.; Nicholls, S. M.; Orpen, A. G.;Vinas, J. M.; Weber, M.; Williams, G. K. J . Organomet. Chem. 1990,394, 385. (c) Bruce, M. I.; Cullen, W. R.; Humphrey, P. A.; bin Shawkataly, 0.;Snow, M. R.; Tiekink, E. R. T. Organometallics 1990,9,2910. @

The methodology used for the experiments described below was essentially the same as that described in earlier papers from these l a b ~ r a t o r i e s . Tris(1-naphthy1)phosphine ~~~ was obtained from Strem Chemicals; the corresponding arsine was prepared from arsenic trichloride and 1-br~monaphthalene.~ Pyrolysis of OSQ(CO)I~ with As(l-CloH7)s. A solution of Os3(CO)12(200 mg, 0.22 mmol) and As(l-C10H7)3 (90 mg, 0.20 mmol) in octane (40 mL) was refluxed for 25 h. TLC revealed the presence of at least 10 products, while IH NMR spectroscopy showed only two major hydride resonances at -17.69 and -21.65 ppm. The reaction solvent was removed in vacuo, and the residue was chromatographed on silica with 41 petroleum ethedCHzCl2 as eluent. The major second band (65%) contained complex 5. Crystals of 5 suitable for X-ray structure analysis were obtained from a 2/1 hexane/CH&lz solution. 5: yellow solid; 'H NMR (400 MHz) 6 8.51 (m, lH), 8.45 (m, lH), 8.20 (m, lH), 8.03 (m, 2H), 7.93-7.82 (m, 3H), 7.79 (m, lH), 7.70 (m, lH), 7.50-7.38 (m, 5H), 7.38-7.31 (m, 3H), 7.27 (m, lH), -17.69 (s, lH, Os satellite, &-Os1 = 27.6, JH-O~Z = 43.8 Hz), -21.65 (s, l H , Os satellite, &-Os1 = 28.0, JH-O~Z = 45.6); mass spectrum (FAB) m/e 1252 (P+,base peak), 1224, 1196, 1167, 1138, 1110, 1094, 1080, 1066, 1052, 1037, 1024, 982,969,954,940,928,912,898,884,870,856,843,829,703. Anal. Calcd for C38HZ1As080s3:C, 36.48; H, 1.69. Found: C, 36.55; H, 1.74. Pyrolysis of R w ( C 0 ) l with ~ As(l-CloH7)s. A solution of triruthenium dodecacarbonyl(128 mg, 0.20 mmol) and As(1C10HT)S (95 mg, 0.21 mmol) in cyclohexane (30 mL) was refluxed for 10 h. 'H NMR spectroscopy revealed the presence (3)Cullen, W. R.; Rettig, S. J.; Zheng, T. C. Organometallics 1992, 11, 928. (4) (a) Cullen, W. R.; Rettig, S. J.; Zhang, H. Organometallics 1991, 10,2965. (b) Cullen, W. R.; Rettig, S. J.; Zhang, H. Organometallics 1992,11,1000. (5) Michaelis, A. Justus Liebigs Ann. Chem. 1902,321,242.

0276-7333/95/2314-1466$09.00/0 0 1995 American Chemical Society

Naphthyne: Os and Ru Cluster Derivatives

Organometallics, Vol. 14, No. 3, 1995 1467

of two hydrides of equal intensity. The solvent was removed Table 1. Crystallographic Data" in vacuo, and the residue was chromatographed on silica with 5 11 compd 41 petroleum etherlCHzCl2 as eluent. The first band gave Ru3formula C ~ ~ H Z I A S O ~ O SC ~~IHI~ASOIIRU~ (C0)lz (5%). The third and major band contained complex 7 fw 1251.10 1040.64 cryst syst monoclinic triclinic (70%);the fourth band contained trace amounts of 11, which spaFe group c2/c P1 on evaporation afforded crystals and which was identified only a, A 25.746( 1) 11.433(3) by X-ray crystallography. b, 8, 9.688(2) 14.746(2) 7: yellow solid; 'H NMR (200 MHz) 6 8.46 (m, 2H), 8.08 (d, c, 8, 33.521(1) 9.958(1) lH), 8.02 (d, lH), 7.91 (m, 2H), 7.86-7.72 (m, 4H), 7.58 (m, a, deg 90 96.91(1) lH), 7.44-7.14 (m, 8H), -15.93 (s, lH), -20.35 (s, 1H); mass P, deg 108.647(3) 102.34(2) spectrum (FAB) mle 984 (P+,base peak), 956, 928, 900, 871, Y deg 90 78.69(2) 7922(2) 1602.9(6) 843, 815, 787, 759, 630. Anal. Calcd for C ~ ~ H Z ~ A S OC, ~ R U ~ :v, A 3 Z 8 2 46.40; H, 2.15. Found: C, 46.57; H, 2.09. ecalc, g/cm3 2.098 2.156 Pyrolysis of O S ~ ( C Owith ) ~ ~ P(l-CloH&. A solution of F(000) 4592 992 Os3(CO)12 (180 mg, 0.19 mmol) and P(l-C10H,)3 (80 mg, 0.19 p , cm-' 104.81 29.33 mmol) in octane (30 mL) was refluxed for 24 h. TLC revealed cryst size, mm 0.25 x 0.30 x 0.35 0.10 x 0.15 x 0.30 the presence of more than eight products. 31PNMR spectrostransmissn factors 0.62-1.00 0.79- 1.OO scan type w w-28 copy revealed three major resonances at 51.1, 42.4, and 30.9 1.04 + 0.35 tan e scan range in w , deg 1.31 + 0.35 tan e ppm, and a number of minor ones. The reaction solvent was 16 (up to 8 rescans) 32 (up to 8 rescans) scan speed, deg/min removed in vacuo, and the residue was chromatographed on data collected +h,+k,&l +h,+k,fl Florisil with 3/1 petroleum etherlCKzClz as eluent. The first 28,,,, deg 60 60 band contained unreacted Os3(CO)12 (3%),identified by TLC cryst decay, o/c negligible negligible and microanalysis. The fourth, fifth, and sixth bands contotal no. of reflns 12 461 9766 tained complexes 6 (35%), 9 (30%),and 10 (lo%), respectively. total no. of unique reflns 12 919 9330 RIllerge 0.044 0.036 6: yellow solid; 31PNMR (121.4 MHz) 6 30.9; 'H NMR (200 no. of reflns with I? 3a(I) 5308 4933 MHz) 6 8.86 (m, 2H), 8.1-6.8 (m, 17H), -17.59 (d, lH, J = no. of variables 452 424 5.6 Hz), -21.47 (d, lH, J = 30.8); mass spectrum (FAB) mle R 0.033 0.030 1208 (Pt,base peak), 1180,1152,1124,1096,1068,1039,1011, R W 0.03 1 0.028 983, 856, 730. Anal. Calcd for C ~ ~ H Z I O ~ OC, S ~37.81, P : H, GOF 1.84 1.42 1.75. Found: C, 37.89; H, 1.79. max N u (final cycle) 0.02 0.001 residual density, e/A3 -0.72 to +1.17 -0.52 to + O H 9: brown solid; 31PNMR (121.4 MHz) 6 51.1; 'H NMR (200 (near Os) ~I MHz) 6 8.3-6.8 (m), -18.53 (d, J = 37.7, satellite, J H - O = 44.0, J H - o = ~ ~31.2 Hz); mass spectrum (FAB) mle 1236 (P+, a Conditions: temperature 294 K, Rigaku AFC6S diffractometer, Mo K a radiation (A = 0.710 69 A), graphite monochromator, takeoff angle 6.0", base peak), 1208, 1181, 1151, 1124, 1095, 1067, 1039, 1011, aperture 6.0 x 6.0 mm at a distance of 285 mm from the crystal, stationary 984, 855, 731. Anal. Calcd for C39H21090~3P:C, 37.92; H, background counts at each end of the scan (scadbackground time ratio 1.71. Found: C, 37.99; H, 1.84. 2/1, up to 8 rescans), u 2 ( p )= [ p ( C 4E)]/LpZ(S = scan rate, C = scan 10: orange solid; 31PNMR (121.4 MHz) 6 42.3; IH NMR count, E = normalized background count), function minimized Ew( IF,, (200 MHz) 6 8.6 (m), 8.2-7.7 (m), 7.6-6.8 (m);mass spectrum IFcIl2, where w = 4FO2/o2(F,2),R = XllFol - IFclI/XIFol.R, = (Xw(lFoI (FAB)m/e 1292 (P+),1264,1236,1208 (base peak), 1181,1153, - IFcl)2/CwIFo12)"2, and GOF = [Cw(lFol - iFc1)2/(m- n)]"2. Values given for R, R,, and GOF are based on those reflections with I Z 30(I). 1125, 1096, 1067, 1039, 1011, 984, 856. Anal. Calcd for c41H210110~3P:C, 38.14; H, 1.64. Found: C, 38.00; H, 1.87. tions in each case. The data were processed6 and corrected Pyrolysis of Ru3(CO)lz with P(l-C10H7)3. A solution of for Lorentz and polarization effects and absorption (empirical, R u ~ ( C O )(130 ~ Z mg, 0.20 mmol) and P(l-C10H7)3(80 mg, 0.20 based on azimuthal scans for 3 reflections). mmol) in cyclohexane (30 mL) was refluxed for 24 h. TLC and 31P NMR spectroscopy revealed the presence of two major Both structures were solved by heavy-atom methods, the coordinates of the heavy atoms being determined from the products and three minor ones. The solvent was removed in Patterson functions and those of the remaining non-hydrogen vacuo, and the residue was chromatographed on silica with 4/1 petroleum etherlCHzClz as eluent. The first band conatoms from subsequent difference Fourier syntheses. In both cases there were space group ambiguities. The structure tained unreacted R u ~ ( C O )(5%). I ~ The second band contained complex 8 (50%). The third band contained complex 12 (E%), analyses were initiated (and successfully completed) in centrosymmetric space groups (C2lc and P1) on the basis of the which was not further identified. number of molecules in the unit cell and the Patterson 8: yellow solid; 31PNMR (81.0 MHz) 6 68.7; 'H NMR (400 functions. All non-hydrogen atoms were refined with anisoMHz) 6 9.05 (m, lH), 8.27-8.15 (m, 2H), 8.10 (d, 2H), 8.04 tropic thermal parameters. One of the metal hydrides of 5 (m, lH), 7.92-7.78 (m, 4H), 7.73 (m, lH), 7.46-7.34 (m, 4H), was included in a difference map position, and the other could 7.30 (m, lH), 7.22 (m, lH), 7.16 (m, lH), 7.07 (m, lH), -15.78 not be located. The carbon-bound hydrogen atoms were fixed (d, lH, J = 5.2 Hz), -19.88 (d, l H , J = 37.4); mass spectrum in idealized positions (C-H = 0.98 A, BH= 1 . B b o n d e d atom). A (FAB) mle 941 (P+),913, 885, 857, 829, 800, 771, 743, 728, secondary extinction correction (Zachariasen isotropic type I) 714 (base peak), 585. Anal. Calcd for C38H2108PRu: C, 48.57; was applied for 5 , the final value of the extinction coefficient H, 2.25. Found: C, 48.66; H, 2.32. being [3.51(7)1 x Neutral atom scattering factors for all 12: pink-brown solid; 31PNMR (81.0 MHz) 6 71.9; 'H NMR atoms and anomalous dispersion corrections for the non(200 MHz) 6 8.30-8.65 (complexm); mass spectrum (FAB)mle hydrogen atoms were taken from ref 7. Final atomic coordi1067 (P+,base peak), 1038,1012,984,956,928,914,900,883, nates and equivalent isotropic thermal parameters are given 872,855, 844,827, 814,800,771, 744, 714,645,615,596, 568, in Tables 2 and 3, and selected bond lengths and angles appear 540, 527, 512. X-ray Crystallographic Analyses of 5 and 11. Crystal(6) (a) TEXSANfl'EXRAY Structure Analysis Package; Molecular lographic data for 5 and 11 appear in Table 1. The final unitStructure Corp., The Woodlands, TX, 1985. (b) teXsan, Crystal Structure Analysis Package; Molecular Structure Corp., The Woodcell parameters were obtained by least-squares refinement on lands, TX, 1985 and 1992. the setting angles for 25 reflections with 26 = 33.5-37.1 and (7) (a) International Tables for X-Ray Crystallography; Kynoch 33.8-38.5", respectively, for 5 and 11. The intensities of 3 Press: Birmingham, England, 1974;Vol. IV,pp 99-102. (b) Internastandard reflections, measured every 200 reflections throughtional Tables for X-Ray Crystallography; Kluwer Academic: Boston, 1992; Vol. C, pp 200-206. out the data collections, showed only small random fluctua9

+

Cullen et al.

1468 Organometallics, Vol. 14, No. 3, 1995 Table 2. Final Atomic Coordinates (Fractional) and Be, Values (ti*)for 5" atom

X

Y

Z

0.235704(14) 0.33844(2) 0.34416(2) 0.17907(3) 0.1581(3) 0.1899(3) 0.4552(4) 0.2949(5) 0.3633(4) 0.4503(3) 0.3232(4) 0.4086(4) 0.2763(3) 0.3196(4) 0.3448(4) 0.327 l(4) 0.2830(4) 0.2622(5) 0.2189(4) 0.1930(4) 0.2111(3) 0.2565(3) 0.1032(3) 0.0905(4) 0.0370(5) -0.0035(4) O.OOSO(4) -0.0338(4) -0.0230(5) 0.0301(4) 0.0724(4) 0.0627(3) 0.1785(3) 0.2 162(4) 0.2247(5) 0.1975(5) 0.1583(4) 0.1297(5) 0.0917(6) 0.0786(5) 0.1059(4) 0.1472(4) 0.1852(4) 0.2068(4) 0.41 1l(5) 0.3114(5) 0.3553(4) 0.4101(4) 0.3302(4) 0.3842(5)

0.53486(4) 0.37428(5) 0.59720(4) 0.63425(9) 0.2962(8) 0.7004(8) 0.2719(12) 0.0940( 10) 0.4995(9) 0.5124(10) 0.8095(11) 0.7661(13) 0.4505(9) 0.3637( 10) 0.2885(10) 0.2977(11) 0.3871(9) 0.4010( 11) 0.4879( 11) 0.5567(9) 0.5454(9) 0.46 13(9) 0.5719(9) 0.4564(11) 0.4046(11) 0.47 14(14) 0.5903( 12) 0.6606(14) 0.7713(14) 0.8201(11) 0.7571(11) 0.6421(10) 0.831l(9) 0.9071(10) 1.0491(11) 1.1112(11) 1.0422(11) 1.1106(12) 1.0419(15) 0.9000( 14) 0.8305( 10) 0.8966( 10) 0.3898(11) 0.6368( 11) 0.3060(14) 0.1976(14) 0.4523( 11) 0.5414( 12) 0.7297( 13) 0.7018(15)

0.074674(11) 0.079042( 12) 0.13 1375(12) 0.11367(3) 0.0464(2) --0.0070(2) 0.1208(3) 0.0436(3) 0.0023(3) 0.1977(3) 0.1913(3) 0.0878(3) 0.1347(2) 0.1363(3) 0.1746(3) 0.2080(3) 0.2071(3) 0.2414(3) 0.2390(3) 0.2034(3) 0.1687(2) 0.1703(2) 0.0958(3) 0.1132(3) 0.1005(3) 0.07 14(4) 0.0521(3) 0.0197(4) --0.0006(4) 0.0095(3) 0.040 l(3) 0.0626(3) 0.1243(3) 0.1 120(3) 0.1207(4) 0.1440(4) 0.1583(3) 0.1822(4) 0.1947(4) 0.1821(4) 0.1595(3) 0.147 l(3) 0.0567(3) 0.0229(3) 0.1051(4) 0.0551(3) 0.0308(4) 0.1729(3) 0.1688(4) 0.1045(4)

B, 3.01(1) 4.01(2) 3.82(2) 2.92(4) 5.9(4) 7.3(4) 10.1(6) 9.4(6) 8.4(5) 8.3(5) 9.5(6) 12.5(7) 2.8(3) 3.7(4) 4.3(5) 4.3(4) 3.3(4) 4.9(5) 4.2(5) 3.4(4) 2.7(3) 2.9(4) 3.2(4) 4.3(4) 5.4(5) 6.1(6) 4.7(5) 6.3(6) 6.4(6) 5.0(5) 4.4(4) 3.3(4) 3.3(4) 4.2(4) 5.5(6) 5.8(6) 4.7(5) 6.3(6) 6.9(7) 6.2(6) 4.3(5) 3.8(4) 3.8(4) 4.6(5) 6.8(7) 6.1(6) 5.0(5) 5.2(5) 5.7(6) 7.37)

Table 3. Atomic Coordinates and Be, Values for 11" atom

X

Y

Z

Be0

Ru(1) Ru(2) Ru(3) Ru(4) As(1) 0(1) O(2) O(3) O(4)

0.71132(4) 0.77466(4) 0.86849(4) 0.79901(4) 0.90783(4) 0.5779(3) 0.4993(4) 0.8266(4) 0.6683(6) 0.9307(4) 0.7629(4) 0.9473(4) 1.1162(4) 0.6731(5) 0.7028(4) 1.0369(4) 0.6795(4) 0.6472(4) 0.5233(5) 0.4340(5) 0.4605(5) 0.3675(5) 0.3942(6) 0.5156(6) 0.6070(5) 0.5838(5) 1.0665(4) 1.1332(5) 1.2473(5) 1.2962(5) 1.2313(5) 1.2796(5) 1.2180(7) 1.1031(6) 1.0526(5) 1.1140(4) 0.6514(5) 0.5779(5) 0.7827(5) 0.7066(7) 0.8703(5) 0.8018(5) 0.9122(5) 1.0259(5) 0.7208(6) 0.7356(5) 0.9466(6)

0.26098(3) 0.12764(3) 0.26004(3) 0.39849(3) 0.24035(3) 0.1000(2) 0.3501(3) 0.1682(3) -0.0182(3) -0.0304(3) 0.3744(3) 0.0758(3) 0.3172(4) 0.5379(3) 0.5023(3) 0.4735(3) 0.2618(3) 0.3266(3) 0.3676(3) 0.3427(3) 0.2785(3) 0.2570(4) 0.2020(4) 0.1649(4) 0.1837(4) 0.2399(3) 0.1895(3) 0.1154(3) 0.0725(4) 0.1042(4) 0.1807(4) 0.2140(5) 0.2864(6) 0.3299(5) 0.2998(4) 0.2252(3) 0.1405(3) 0.3182(4) 0.2047(4) 0.039 l(4) 0.029 l(3) 0.3315(3) 0.1418(4) 0.2937(4) 0.4877(4) 0.4588(3) 0.4479(4)

0.05264(4) 0.24448(4) 0.45879(4) 0.25808(4) 0.22430(5) -0.0027(4) -0.1573(4) -0.1824(4) 0.3435(6) 0.1099(4) 0.6960(4) 0.5878(4) 0.5616(4) 0.4555(5) -0.0005(4) 0.3255(5) 0.3538(5) 0.2540(5) 0.2095(5) 0.2597(5) 0.3624(5) 0.4203(6) 0.5255(7) 0.5788(6) 0.5242(6) 0.4126(5) 0.1815(5) 0.2531(5) 0.2267(7) 0.13 12(7) 0.0590(6) -0.0435(7) -0.1135(7) -0.0902(6) 0.0061(5) 0.0820(5) 0.0638(5) -0.0767(5) -0.0947(5) 0.3117(7) 0.1616(5) 0.6076(5) 0.5322(5) 0.5260(5) 0.3820(6) 0.0924(6) 0.2990(6)

2.829(9) 3.023(9) 2.877(9) 3.040(9) 2.62(1) 5.0(1) 6.4(1) 5.8(1) 10.8(2) 5.5(1) 6.3(1) 6.4(1) 7.0(1) 8.5(2) 6.5(1) 7.1(1) 3.0(1) 3.0(1) 3.5(1) 3.7(1) 3.3(1) 4.3(1) 4.9(2) 4.8(2) 4.0(1) 3.1(1) 3.2(1) 3.7(1) 5.2(2) 5.1(2) 4.0(1) 5.4(2) 6.5(2) 5.8(2) 4.3(1) 3.4(1) 3.5(1) 4.1(1) 3.8(1) 5.9(2) 3.6(1) 3.7(1) 4.2(1) 4.4(1) 5.2(2) 4.1(1) 4.5(1)

O(5)

O(6) O(7) O(8)

O(9) O( 10) O(11) C(l) C(2) C(3) C(4) C(5) C(6) C(7) C(8) C(9) C(10) C(11) C(12) C(13) C(14) C(15) C(16) C(17) C(18) C(19) C(20) C(21) (32.2) C(23) C(24) C(25) C(26) C(27) C(28) C(29) C(30) C(31)

Be, = a/3n2(Ull(aa*)2+ U~z(bb*)~ + 1Y33(bb*)~+ 2Ulzaa*bb*(cos y ) + 2Ul3aa*cc*(cos fi) + 2U23bb*cc*(cos a)). a

which is attached to an arsenic atom coordinated to 041). There are eight terminal carbonyls, three each in Tables 4 and 5, respectively. Hydrogen atom parameters, bonded to 0 4 2 ) and 0431, two to Os(l), and two anisotropic thermal parameters, complete tables of bond bridging hydrides, with only one being located in the lengths and bond angles, torsion angles, intermolecular constructure refinement. The Os(l)-Os(2) bond at 3.0316(6) tacts, and least-squares planes are included as supplementary 8, is the longest, and Os(2)-0s(3) at 2.7564(7)A is the material. Structure factors are available from the authors on shortest. Os(l)-Os(3) has an intermediate length of request. 2.8950(5) A. H(l), which was located, bridges the Os(l)-Os(3) bond, and the other hydride is believed to Results and Discussion bridge the shortest Os(2)-0s(3) bond rather than the Pyrolysis of Os3(CO)12with As(l-C10H7)3in octane for longest Os(l)-Os(2) bond. This argument is based on 25 h affords one major product (5) and some minor ones the fact that in the analogous phosphine complex 6 as judged by TLC. described below the two hydrides show very different Complex 5 gives a parent ion at mle 1252 in the mass couplings to the phosphorus atom, indicating that most spectrum, corresponding t o the formula oSS(c0)8[&likely one hydride is two bonds and the other three (1-C10H7)31. The lH NMR spectrum shows the presence bonds away from the phosphorus atom. The whole of only 19 naphthyl protons and two hydrides; consecluster is electron-precise. The naphthyne moiety is quently, a formulation such as OS~(CO)~(H)~[(~-C~OH?)~bonded t o Os(1) and Os(2) via two u bonds (Os(l)-C(l) &(l-C10H5)1 seems likely. A single crystal structure = 2.112(8), Os(2)-C(2) = 2.128(9) A), and to Os(3) via determination cofirms this formulation, and an ORTEP a q2 bond (Os(3)-C(l) = 2.281(8),Os(3)-C(2) = 2.369(9) diagram of the molecule is shown in Figure 1. A). This bonding mode is very similar t o that found in The molecular structure of 5 consists of a closed Os3 1' and in O S ~ ( C O ) ~ ( H ) ~ ( Cthe G HC(l)-C(lO) ~):~ plane of triangle capped on one face by a naphthyne moiety 5 makes an angle of 63.64' with the Os3 plane; in os3-

Naphthyne: Os and R u Cluster Derivatives

Organometallics, Vol. 14, No. 3, 1995 1469

Table 4. Selected Bond Lengths (A) with Estimated Standard Deviations for 5 and 11 Os( 1)-0s(2) OS(1 ) - 0 ~ ( 3 ) OS(l)-As( 1) Os(1)-C( 1) Os( 1)-H( 1) 0~(2)-0~(3) Os(2)-C(2) Os(3)-C(l) 0~(3)-C(2)

Compound 5 3.0316(6) Os(3)-H(l) 2.8950(5) C(3)-C(4) 2.446(1) C(4)-C(5) 2.112(8) C(5)-C(6) 1.61 C(5)-C( 10) 2.7564(7) C(6)-C(7) 2.128(9) CV)-W) 2.281(8) W)-W) 2.369(9) C(9)-C( 10)

Ru(l)-Ru(2) Ru( 1)-As( 1) Ru(Z)-As( 1) Ru(3)-As( 1) Ru(4)-C(2) C(l)-C(2) C(2)-C(3) C(4)-C(5) C(5)-C( 10) C(7)-C(8) C(9)-C( 10) Ru( 1)-Ru(4)

Compound 11 2.7892(7) Ru(l)-C(2) 2.505l(8) Ru(2)-Ru( 3) 2.5146(7) Ru(2)-C(1) 2.4445(6) Ru(3)-Ru(4) 2.195(5) Ru(3)-C(l) 1.403(6) Ru(4)-As( 1) 1.424(6) C( l)-C(lO) 1.421(7) C(3)-C(4) 1.418(7) W)-C(6) 1.401(8) C(6)-C(7) 1.414(7) C(8)-C(9) 2.8704(7)

1.87 1.34(1) 1.42(1) 1.42(1) 1.40(1) 1.38(1) 1.34(1) 1.39(1) 1.41(1) 2.320(4) 2.8934(7) 2.330(4) 2.9062(7) 2.187(5) 2.4399(6) 1.450(6) 1.355(7) 1.414(7) 1.348(8) 1.363(7)

13

C 14

c27

Table 5. Selected Bond Angles (deg) with Estimated Standard Deviations for 5 and 11 Os(2)-Os( 1)-0s(3) 0 ~ ( 2 ) - 0 ~1)-As( ( 1) Os(2)-Os( 1)-C( 1) Os(2)-Os( 1)-c(31) Os(3)-0s(l)-C( 1) Ru(~)-Ru(1)-R~(4) Ru(~)-Ru(~)-Ru(~) Ru(l)-Ru(2)-Ru(3) Ru(1)-As( 1)-Ru(4) Ru(2)-As( 1)-Ru(3) Ru(2)-C(l)-Ru(3)

Compound 5 55.37(1) Os(l)-Os(2)-0~(3) 146.76(3) Os(l)-Os(2)-C(2) 66.2(2) C(2)-C(l)-C(lO) 97.8(3) C(l)-C(2)-C(3) 51.4(2) Os(l)-Os(3)-0~(2)

59.80( 1) 67.7(3) 120.2(8) 118.2(8) 64.83(1)

Compound 11 91.14(2) Ru(2)-C(l)-C(2) 88.37(2) Ru(2)-C(l)-C(lO) 91.18(2) Ru(3)-C(l)-C(lO) 70.95(2) Ru( l)-C(2)-Ru(4) 71.37(2) Ru(l)-C(2)-C(3) 79.6( 1) Ru(4)-C(2)-C(3)

104.7(3) 109.5(3) 125.9(3) 78.9(1) 104.4(3) 122.8(3)

Figure 1. ORTEP diagram for 5 (33%probability thermal ellipsoids). (l-C1oH5)1. Complex 6 undoubtedly has the same basic structure as 5.

M

(CO)g(H)2(C6H4)the corresponding angle is 63.9 (and 69.0°).8 The torsion angle Os(2)C(2)C(l)Os(l)is 64.7”, with 041)and 0 4 2 ) on opposite sides of the naphthyne plane a t distances of 0.230 and 0.048 A, respectively. In naphthalene the C-C bond lengths are of three types, as follows (using the numbering shown in Figure 1): “C(l)-C(2)” “C(3)-C(4)”, “C(6)-C(7)”, and “C(8)C(9)”, 1.377(2) “C(2)-C(3)”, “C(7)-C(8)”, 1.411(2)A; the remainder, 1.424(2)A.g This pattern is seen in the bond lengths of the naphthyne moiety of 5 with no apparent difference bein observed for the V2-bound C(l)-C(2) bond (1.38(1) 1, although the data are not good enough for much comment. The shortening of C(7)-C(8) t o 1.34(1) A may be unusual. Pyrolysis of O S ~ ( C Owith ) ~ ~P(l-C10H7)3in octane for 24 h affords more than eight products with three (6,9, 10)in major quantities, as judged by TLC and 31Pand lH NMR spectroscopy. Complex 6 shows a 31PNMR resonance at 30.9 ppm, suggesting the presence of a phosphine. The lH NMR spectrum shows complex resonances in the aromatic proton region and the presence of two hydrides. The hydride chemical shifts are very similar to those of 5. The mass spectrum (parent ion a t mle 1207) and the microanalysis are consistent with the formulation Os3(C0)8(H)2[(1-CloH7)2P-

k;

1

(8) Goudsmit, B. T.; Johnson, B. F. G.; Lewis, J.; Raithby, P. R.; Rosales, M. J . J. Chem. SOC.,Dalton Trans. 1983,2257. (S)Ponomarev, V. I.; Filipenko, 0. S.; Atovmjan, L. 0. Kristallografiya 1976,21,392.

E

5 Os As 60s P 7 Ru As

9

8Ru P

F’yrolysis of RUB(CO)IS with AS(l-C10H7)3in cyclohexane for 10 h affords one major product, complex 7. This derivative shows a complex ‘H NMR spectrum, but a 2D proton-proton correlation NMR study supports the presence of 19 naphthyl protons with one unique naphthyl group containing only five hydrogen atoms. The two hydride resonances are similar to those of the osmium naphthyne complexes 5 and 6, and the mass spectrum gives the parent ion at mle 984, consistent with the formula R u ~ ~ C O ~ ~ ~ H ~ ~ ~ ~ 1 - C ~ o H ~ ~ 2 A s ~ The structure of 7 is undoubtedly analogous to that of 5. Likewise, complex 8, obtained from the reaction of RU~(CO)I~ with P(l-C10H7)3,shows spectroscopic properties that are consistent with formulation as the naphthyne complex RU~(CO)~(H)~[(~-C~~H~)~P(~-C~OH Compounds 7 and 8 are not only the first naphthyne complexes of a ruthenium cluster to be isolated, they are also the first aryne complexes of a ruthenium cluster known t o have a structure analogous to the osmium benzyne derivative O S ~ ( C O ) ~ ( H ) ~ (discussed C ~ H ~ ) above. It is interesting to note that naphthyne complexes of this structure are formed in all the reactions of M3(C0)12 (M = Ru, Os) with E(l-C10H7)3(E = P, As). This is a rare example of a series of complexes in both Ru3 and Os3 systems with both phosphorus- and arsenic-based ligands. The best known series of benzyne complexes

Cullen et al.

1470 Organometallics, Vol. 14, No. 3, 1995

for both Ru3 and Os3 systems is M~(CO)~(C~H~)(ERZ)Z of structure 1; however, the combination M = Ru, E = As is unknown a t this present time.l The naphthyne complexes from As(l-C10H7)3 are formed in higher yield than from P(l-C10H7)3for both the Os3 series (65%compared to 35%)and the RUBseries (70% compared to 50%). This may correlate with the increased length of the h-ClOH7 bond. Complex 9, obtained from the reaction of Os3(CO)12 with P(l-C10H7)3,shows a 31PNMR resonance at 51.1 ppm, suggesting the presence of a phosphine. The lH NMR spectrum is very complex between 6.8 and 8.3 ppm, but a hydride resonance a t -18.53 ppm is present. The mass spectrum gives a parent ion at mle 1236 correspondingto the formulation OS~(CO)~(H)[(~-C~OH~)ZP(~-C~O&)]. The hydride chemical shift is similar to that of related aryl complexes such as Os3(CO)g(H)[(C5&8 PPhC6H4)Fe(C5H5)ll0and OS~(CO)~H(PM~P~(C~H~),~~ and a corresponding structure is proposed. This complex would be formed via an initial ortho-metalation reaction. Complex 10, isolated from the same reaction mixture, shows a 31PNMR resonance at 42.4 ppm, suggesting the presence of a phosphine. The IH NMR spectrum again is very complex. The mass spectrum gives the parent ion at mle 1292, consistent with the monosubstituted complex O S ~ ( C O ) ~ ~ [ P ( ~ - C The ~OH~)~I. microanalytical data are in accord. C17 C16 Ortho-metalation reactions such as that leading to 9 are believed to be the first step in the formation of Figure 2. ORTEP diagram for 11 (33% probability thercluster-bound arynes such as 1-4: cluster-assisted mal ellipsoids). P(As)-C bond cleavage completes the reaction. However, P(As)-naphthyl cleavage does not seem to be a a six-electron donor comprising two u plus two q2 major reaction pathway largely because of the ready interactions. formation of 5-8, and only a few crystals of a complex The naphthyne in 11 seems to be a four-electron donor (11) in which As-C cleavage did occur were isolated. to the cluster, as is the aryne in 1, 3,and 6;however, The structure of 11 is shown in Figure 2. in 11 the four electrons are supplied via four u bonds, The aryne moiety in 11 is bound t o one side of a Ruq whereas in the others the source is two u and one q 2 plane and an arsinidene to the other. The resemblance bond. This model formally makes 11 electron deficient, to the benzyne derivative 2 is immediately apparent; as there is nothing in the other metrical data to indicate however, there are important structural differences. an alternative source of these electrons, in contrast to First, the naphthyne sits a t an angle of 75.3" to the the situation found in 4, where Cr-Ru bonds are metal plane. This is much closer to 90" than is found unexpectedly present. in any other aryne of structure 1 or 2. For example in 2 the dihedral angle between the benzyne and the Ru4 When the C-C bond lengths of the naphthyne moiety plane is 51.1".2 Second, in 2 two of the ruthenium atoms of 11 are compared with those of naphthalene, listed lie close to the benzyne plane (0.056 and 0.027 A); i.e., above, the shortest bonds in 11 are as expected C(3)they are almost coplanar with the aryne. In 11 Ru(3) C(4) (1.355(7)A), C(6)-C(7) (1.348(7)A), and C(8)-C(9) and Ru(4) lie respectively 0.767 and 0.976 A from the A), with the exception of C(l)-C(2) (1.403(6) (1.363(7) naphthyne plane. Third, Ru(4)-C(2) (2.195(5) A) and A), whose length has increased as a consequence of the Ru(3)-C(1) (2.187(5)A) are longer than the correspondp4 bonding. Other changes are less significant; for ing bonds in 2 (2.116(6) and 2.119(6) &, and the pair example, the lengths of the pairs C(2)-C(3) (1.424(6) Ru(2)-C(1) (2.330(4) A) and Ru(l)-C(2) (2.320(4) A) A)and C(7)-C(8) (1.401(8)A)are much the same as in seem to be slightly longer than the corresponding bonds naphthalene (1.411(2)A). in 2 (2.306(6) and 2.317(6) A). The net result of this increase in tilt angle and bond lengths of 11 is that the distances Ru(2)-C(10) and Acknowledgment. We thank the Natural Sciences Ru(l)-C(3) a t 3.199(5) and 3.256(5) A are too great t o and Engineering Research Council of Canada for finanpermit any significant bonding interaction. In 2, where cial support. there is q2 interaction, the equivalent distances are 2.625(7) and 2.612(7) A. Thus, it seems that the Supplementary Material Available: Tables of hydrogen bonding of the naphthyne moiety in 11, unlike the atom parameters, anisotropic thermal parameters, all bond benzyne in 2, is not satisfactorily explained in terms of

&

(10) Cullen, W. R.; Rettig, S. J.; Zheng, T. C. Can. J. Chen. 1992, 70, 2215. (ll)Deeming, A. J.; Kabir, S. E.;Powell, N. J.; Bates, P. A.; Hursthouse, M. B. J . Chem. SOC.,Dalton Trans. 1987, 1529.

lengths and bond angles, torsion angles, intermolecular contacts, and least-squares planes for 5 and 11 (42 pages). Ordering information is given on any current masthead page. OM9408425