ELSEVTER

§yntheses of indenyl lanthanide derivatives and the molecular structures of [(C,H,/,PrC1(THF)]2 and [(C,H,),La(THF)]

Q i Shen a- * , Minhua Qi “, Sheping Song ‘, Lilu Zhang ‘l, Yonghua Lin b

Journul of Organometlrllic Chemistry 5-W ( 1997) 9S- l(H)

Received 23 April 1997: received in revised form 5 August I997

Abstract

The reaction of anhydrous PrCl 3 with Na(C,)H 7) in I :2 mole ratio in THF $ves [(C,,H, )ZPrCI(THFJJ1 1. 1 crystallized in monoclinic system. space group P2 ,/c with LI = 7.808(2), h = I7.796(6). (* = I4.070(4! A. /3 = 93.97(Z)“. V = 1950.3(9) A-3, Dcalcd = I .63 g/cm3

and % = 2. Each Pr ion is surrounded by two indeayl. two Cl and one THF in ;I roughly trigonal bipyramid arrangement with average

Pr-C(ring) and Pr-Cl distances of’ 2.81 and 2.Hq A. The reaction of LaCl 3 with Na(C,>H 7) in I :3 moie ratio gives (C,H,),l.aTHF 2, which crystakes in the monoclinic space group P2,/a with unit cell constants (1 = 21.X71(8), h = 10.585(3). ~8 = 23.652(7) i

p = I l-l.62(2)“, V = 4977.9 A’ and Z = 8. 0 1997 Elsevier Science S.A.

Kqwrwd.s: Ltlntham~; Praseodymium: Indenyl; X-ray diffraction; Synthesis

1. Introduction

Indene is II versatile auxiliary ligand used in synthe- sis of orgunomctallic compounds. The first triindenyl lanthanides (C,,H 7 ),LnTHF (Ln = La, Sm, Gd, Tb, Dy, Yb; [I ,Z]) were rcportcd lo be synthesized from fhe reaction of LnCl I with Na(C,,H,) in I :3 mole rho in 1969. However, no corresponding crystal structure was obtained whereas an ion-pair coin plex [N~(THF),][Ln(rl”-(C,,H,), ( @I)Ln($-C,H,),] was isolated and structurally characterized from this reaction [WI. By the reaction of LnCI, with stoichiometric amounts of Mg(C,H 7 j2 [5] or K(C,H 7) [6], an unsol- vated (C,H, ),Ln was prepared and the molecular struc- ture of Sm complex was determined. Later, the crystal structures of (C,H, I,, Ln THF (Ln = Nd, Gd), which were synthesized from the reaction of LnCI,, K(C, H 7) and K ,(C,H,) as byproducts, were published [7].

Compared with triindenyllanthanide complexes, in- denyllsnthanide chlorides are poorly characterized until now, although indenyllanthanide chlorides are the use- ful precursors for further transformation. With bulky substituted indenyl, heptamethylindenyl, as a ligand,

* Corresponding author.

heptamethylindenyl complexes of lanthanids, (C, Me, 1, LnCI ,+ ,# (Ln = La, Er, Nd: 11 = l-3). were conveniently synthesized [IS]. Ho,vrver, for unsubsti- tuted indenyl complex there is only (C,,H 7 )“rdCI,(THF), reported in the literature [9]. We

Table I Crystalloprrrphic data ol‘ complexes 1 and 2

Formula Crystal system

C,,H,.+Cl,Pr,O, monoclinic

C 3, H >,,OLa monoclinic

Spice g&up Cell constants

u. A

h. ii f’, A 89 o 1’. A’ z IA.. g/cm ’ SCarI range. 2 0 p. cm-’ F(W) Retlections Retlections for I -1 3rr(l) R RW

P2, /c

7.8013(2)

I7.79hfh)

I4.070(4) 93.97(Z)

1950.3(9) 3 i I .63 3-40 26.3 I 952 2092 I Oh9 0.045 0.039

P2, /u

21.X71(3

10.585(3

23.652(7 I l4.62(2

4977.94 H I .a 3-50 17.59 2240 7885 6460 0.053 0.056

W22-328X/97/$17.00 0 I997 Elsevier Science S.A. All rights reserved. PI/ SOO22-32Xx(97)00496-X

&+-TL’“’ C(7)

Fig. I. The molecule structure of complex 1.

have recently synthesized THF-solvated diindenyl praseodymium chloride [(C,H, J2 PrCI(THF)], 1 and de- termined its molecular structure. To our knowledge, this is the first structure for this kind of complex. In this paper we also like to report the synthesis and molecular structure of (C,,H, ),La THF 2.

2. Experimental

All manipulations were conducted under Ar using standard Schlenk techniques. THF was distilled from solutions of sodium benzophenone ketyl. lndene (Fluka)

was dried over 4A molecular sieves and was distilled before use. Na(C,H,) was prepared from Na and in- dene in THF. Anhydrous LnCI, (Ln = Pr, La) was prepared by published method [lo]. C,D, was dried over Na and was vacuum-distilled. ‘H NMR spectra were obtained on Varian 400-MHz NMR spectrometer. IR were recorded on a ALPHA Fourier infrared spcc- trometer as KBr pellet.

Into the reaction tlask containing PrCl, ( I .Y4 g, 7.6 mmol) and 40 ml THF was added 8.90 ml ( I .73 M) of

Fig. 2. The molecular structure of complex 2.

Table 2 Atomic D coordinates ( X 10’ ) and quivulrn~ temperature lactors

( X IO’ A) for non-hydrogen atom,\ of complex I

Atom X Y Z u,,, Pr 7-w(2) Cl 1662(6) C(I) 4291(21) C(2) 4024c I 1 C(3) 3 I 73(25 1 C(4) 3083( IO) C(5) 376222) C(6) 3946(2-l 1 C(7) 3335(25) C(8) 2697(23) C(9) 255 I(221 0 -%I(131 C(II) - 1887(23) C(l2) - 2243(26) C(1.J) - 16X3(39) C(l4) - I 15X(34) C(21) - Il85(32) C(22) - 1812(23) Cc+) - 355(25 1 cc41 X51(21) C(25) 379W) C(26) I560(37) U-37) 311003) C(28) 3392(29) C(29) 2517W)

5924( I 1 5216(3) 5758( IO) 643l(ll) 6287( IO) 5475( IO) 5133(1 I) 433l(lO) 3889( I I ) 4215(12) 3991( 12) 5884(7) 5239( I I) 537% I I ) 6157(12) 6543( 12) 72sN I I 1 68541 IO) 6795(C)) 7150( IO) 7529( IO) X066( I 2 1 X231(13) 7932( 13) 7396( 12)

60X7( I 1 3359(3) 6179( 14) 6737( 16) 7547( I 3 ) 7667( I I ) 6813(13) 6643( 14) 7357( 16) 81X1(16) 8297( I 3 1 7548(7) 7873( I I ) K957( 14) 9062( I 7 1 8215( 16) 6OSl( 14) 5264( I 5 1 46Ol( 13) 5007( I 2 1 5933( 1-I) 6450(17) 6006( 25) 50X7( IX) 46:U I 7 1

33(l) 5(#2) 57(S) s3w 62W 40(7) 49(8) 61(g) 87( IO) 89( IO) 70(8) 56(4) 61(X) 72(c)) 13l(lS) lOh(l2) 65(C)) 6210 61(8) -w(7) S4(8) lO(Kl2) l54( 17) 134(13) 122(12)

Na(C,H,). The mixture was stirred for 3 days at about 70°C. After centrifuc 0. ,:ion to remove NaCl precipitate, the solution was concentrated to IO ml and crystallized at room temperature. The yellow-green crystals of 1 were obtained (2.50 g, 68.8%). Elemental analysis: Found: Pr, 20.40; C, 54.24: H, 4.60: Cl, 7.57%. Calcd. for C,, H,,CI , Pr,O,, Pr, 29.45; C, 55.18; H, 4.60; Cl, 7.42. IR(cm= 1: 3060(m), 3030(m), 2965(s), 2862(s). 1675(s). 1602(s), 1450(s), 1390(m), 1358(m), 1060(s). 1038(m), 1010(m), 940(m), 910(w), 855(w), 760(s). 7 IO(s), 690(w).

2.2. Pt-qw~ltiotl ~~f’cYmpliJx 2

LaCl, ( 1.2 g, 4.89 mmol) was placed in a Schlenk flask. THF solution of Na(C,H,) ( I9 ml, 14.67 mm& was added. After stirring for 24 h at room temperature. the mixture was centrifuged to remove NaCl and the solution was concentrated until to slightly turbid. then placed for crystallization at - 10°C. Very pale crystals were isolated ( I .9S g, 71.7%) m.p. l8S-190°C. Elemen- tal analysis, Found: C, 66.28; H, 5.15; La, 24.54%. Calcd. for C,,H,,jOLa C, 66.91; H, 5.25; La, 24.98% IR(cm- I): 3061(m), 2886(m), 1677(m), 1602(m), 1457(m), 1392(m), 1292(m), 1069(m), 1016(m), 914(m), 861(m), 766(s), 718(m), 694(m), 550(m). ‘H NMR (C,D,)ppm: 3.18(t,l), 5.91(6,2), 7.15U,2), 7.35( d,2)(indenyl); 1.29, 3.29 (THF).

3. Determination of crystal structure

A yellow green crystal with dimensions of 0.28 x 0.34 X 0.41 mm was sealed in a thin walled lithium glass capillary. The intensity data were collected on a Nicolet R3M/E four circle diffractometer using graphite monochromated MoK a radiation in the W-2 8 scan mode with 3” I 28 I 40°, 2092 reflections were col- lected, 1069 reflections with I> 3 a(l) were consid- ered observed. The intensities were corrected for LP and absorption factors. A summary of data collection parameters is given in Table I.

All calculations were carried out on an Eclipse S/ 140 micro computer with the SHELXTL computer program system. The position of the heavy atom was found from Patterson methods. All the non-hydrogen atoms were revealed by successive Fourier and difference Fourier syntheses. The coordinates of hydrogen atoms were determined according to theoretical modes. Further re- finement led to final convergence of R = 0.045 and RbV = 0.039.

3.2. Cotnples 2

A very pale crystal with dimensions of 0.26 X 0.36 x 0.34 mm was sealed in a thin-walled lithium glass capillary. 7885 reflections with 3” ,< 2# ,< 52” in the W-2 6 scan mode were collected, 6460 reflections with / 2 3(7(I) were considered observed. The intensity data collection and structure resolution are as same as men- tioned above. A summary of data collection parameters is given in Table I, Further refinement led to final convergence at K = 0.053, Hlz* = 0.056.

4. Results and discussion

PrCI, reacted with Na(C, H 7) in I :2 mole ratio giving complex 1 in good yields. Attempt to prep:&re the analogous complexes with Nd. La. and Ce failed.

PrCI, + 2Na( C,HI)

= [(C,H,),PrCl(THF)]2 + 2NaCI I

(1)

LaCI 3 reacted with 3 equivalents of Na(C,H,) to fornl CotnpIcx 2 as very pale crystals in good yields. although ion-pair complexes formulated as [Na(THl;),‘q[L11(C,,H,),ClLn(C,H7),] are often isolated by the same reaction [3,41.

LaCI, + 3Na(C,H,) = (C,H,),LaTHF + 3NaCl 7 - (2)

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loo

istry of Shanghai Institute of Organic Chemistry, Chi- nese Academy of Sciences for the financial support.

[S] J.L. Atwod. J.H. Burns. P.G. Lauhereau. J. Am. Chem. Sec. 95 (1973) 1x30.

[6] R.K. Sharma. C.P. Sharma. J. Indian Chem. Sot. 64 (1987) 506. [7] J.S. Xia. Z.G. Jin. Q.Y. Lin. W.Q. Chen. J. Organomet. Chem.

408 (I991 1 173.

References

[I] M. Tsutsui, H.J. Gyslin,, n J. Am. Chem. Sot 91 (1969) 3175. [2] M. Tsutsui. H.J. Gysling. J. Am. Chem. Sot. 90 (1968) 6880. [3] M. Chen. G. Wei. W. Wu. S. Zhuang. Z. Hwng. Organometallics

7 (1988) 802. [J] Y. Su, Z.S. Jin. N.H. Hu. W.Q. Chen. Proc. 25th ICCC.

Nanjing. China, 1987. p. I-Cl.

[8] M. Tsutsui. L.-B. Chen. D.E. Bergbreiter, T.K. Miyamoto. J. Am. Chem. Sot. 104 ( 1982) 855.

[9] G. Fuxing. W. Gecheng. J. Zhongsheng. C. Wenqi. J. Orgunomet. Chem. 43X (1992) 289.

[IO] M.D. Taylor. C.P. Carler. J. lnorg. Nucl. Chem. 24 ( 1962) 387. [I I] Z.S. Jin, Y. Lin. W.Q. Chen. Sci. Sin. I (1987) I. [I?] J.Z. Jin. Z.S. Jin. W.Q. Chen. Jiegou Huaxue I I (1992) 204. [ 131 R.D. Shannon. Acta Crystallogr. Sect. A 32 ( 1976) 75 I. il.41 J.H. Burns, P.G. Laubereau. Inorg. Chem. IO (1971) 2789. [IS] A. Zazzetta. A. Grew. Acta Crystallogr. B 35 ( 1979) 357.