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J. CHEM. SOC. DALTON TRANS. 1992Dalton Communications1751Reactions of Co-ordinated Phosphines and Arsines.Iron( 11)-facilitated Syntheses of I -Phenylphosphetaneand 1 -PhenylarsetaneArmin Bader, Devendra D. Pathak, S. Bruce Wild" and Anthony C. WillisResearch School of Chemistry, Australian National University, Canberra, ACT 2607, AustraliaPhenylphosphine in the complex (R",R")-( +)-[Fe(q-C,H,){C,H,(PMePh),-I ,2}(PH,Ph)] PF, wastreated with 1,3-dibromopropane in the presence of KOBu' to give 1 -phenylphosphetane; similarly, ( ) -(3-chloropropyl)phenylarsine was converted into 1 -phenylarsetane.The cyclooligomerization of epoxides by various metalcompounds into crown ethers presents the tantalizing prospectof a facile and perhaps stereoselective synthesis of a macrocyclicpoly(tertiary phosphine or arsine) by a similar strategy.Macrocycles of this type, which contain pyramidally stablephosphorus or arsenic stereocentres, are difficult to obtain inconfigurationally homogeneous form by classical methods.'Hitherto, however, there has been no experimental evidenceconcerning the parent phosphorus-substituted phosphetanes1,3 and the synthesis of free arsenic-substituted arsetanes 2 bythe previously published procedure is currently beingreinvestigated (since deprotonation of free ( +)-(3-chloro-propy1)phenylarsine leads to extensive oligomerization of theintermediate arsenide).Accordingly, we have performed metal-template syntheses of 1-phenylphosphetane 1 (R = Ph) and 1-phenylarsetane 2 (R = Ph) with the view to establishing routesto the co-ordinated molecules and the structures of thecomplexes.Thus 3-0.5CH,C12,5 when treated with 173-dibromopropaneand 1,8-diazabicyclo[5.4.O]undec-7-ene in tetrahydrofuran(thf), affords complex 4.The salt was isolated in 85% yield asfriable yellow needles of the hemidichloromethane solvate4-0.5CH2C12,t or, in considerably lower yield as the fractionalmixed solvate 4-0.75C6H6*0.25CHCI,. Crystals of the latterform of the complex were suitable for X-ray crystallography.$t Selected spectroscopic data for 4*0.5CH2C1,. NMR: 'H (300 MHz,CD,Cl,, standard SiMe,) 6 0.85-2.40 (6 H, m, CH2CH,CH,), 2.0913 H, d, I'J(PH)I 8.2, PMe], 2.43 [3 H, d, I2J(PH)I 8.8 Hz, PMe] and6.70 8.00 (19 H, m, aryl H); I3C (75.43 MHz, CDCI,, standard SiMe,)6 23.36 [d, 12J(PC)I 18.5, CH,CH,CH,], 25.79 [d, I'J(PC)I 31.9,CH,CH,CH,] and 28.56 [d, I'J(PC)I 34 Hz, CH,CH,CH,]; 31P(121.42 MHz, CDCI,, standard H,PO,) &(PA) 79.70, 6(PB) 80.73 and6(P,) 99.47 [m, ABX system, I2J(PAPB)l 44.2, 12J(PAPx)I 50.7, IzJ(PBP,)I49.2 Hz].Crystai duru jor 4.0.75C6H6.0.25CHC1,: C38.,5H4,,7,C1,,75F6FeP4,M , = 826.82, dark brown crystals from benzene-chloroform; spacegroup P2,/n, a = 22.491(14), b = 14.477(14), c = 25.516(17) A, p =112.55(5)", Li = 7673(10) A3, 2 = 8, D, = 1.431 g cm-,, Mo-Karadiation (A = 0.710 73 A), graphite monochromator, p = 6.6 cm-'.Data were collected at - 125 "C on a Nicolet XRD P3 diffractometer.A total of 13 243 unique reflections were recorded in the range 2 <28 G 50", of which 3484 with Z > 30(Z) were regarded as observed.Thestructure was solved by direct methods and refined by a full-matrixleast-squares procedure, R = 0.087.Atomic coordinates, bond lengths and angles, and thermal para-meters for both structures have been deposited at the CambridgeCrystallographic Data Centre. See Instructions for Authors, J. Chem.Soc., Dalton Trans., 1992, Issue 1, pp. xx-xxv.0--R1Qs-R23 4The phenylarsine analogue of complex 3 could not be pre-pared by the method used to prepare complex 3 itself, indeed,well characterized transition-metal derivatives of primaryarsines are rare.6 The secondary arsine complex 5, however,which was prepared from ( & )-(3-~hloropropyl)phenyIarsine,~is readily isolated,§ and deprotonation of 5 with KOBu' in thf'affords complex 6 in high yield.? The crystal structure of 6 hasbeen determined.11The molecular structures of the cations in complexes 4and 6 are shown in Figs. 1 and 2, respectively. The 1-phenylphosphetane complex crystallizes with two independentmolecules of C , symmetry in the unit cell. The structural$Complex 5 was obtained as a mixture of two diastereomers from(R*,R*)-( & )-[Fe(q ,-C,H ,){ C6H,( PMePh),- 1 ,2}(NCMe)]PF6 (7.95mmol) and (+)-HAs(Ph)[(CH,),CI) (10 mmol) in boiling ethanol.NMR: P ( 121.42 MHz,CD,CI,,standard H3P04) &(PA) 83.3 and 6(PB)80.7 [2 d, AB system, IzJ(PAPB)l 44.01, &(PA) 83.0 and 6(PB) 81.8 [2 d, ABsystem, 12J( PAPB)I 43.5 Hz]; fast atom bombardment (FAB) massspectroscopy m/z 673 (C,,H,,AS~~CI~~F~P,, M').Satisfactoryelemental analysis was obtained.Ti Selected spectroscopic data for 6. NMR (CD,Cl,): 'H (300 MHz,standard SiMe,) 6 1.2-2.6 (6 H, m, CH,CH,CH,); I3C (75.43 MHz,standard SiMe,, arsetane ring) 6 26.23, 26.14 and 24.41; 31P (121.42(MHz, standard H3P04) 6(PA) 82.1 and 6(P,) 80.9 [2 d, AB system,12J(PAPB)I 44.6 Hz]; FAB mass spectroscopy m/z 637 (C3,H36As56FeP,,11 Crystal data for 6: C,,H,,AsF,FeP,, M, = 782.34, orange-redprisms from dichloromethaneciiethyl ether; space group P2,2,21; a =D, = 1.512 g ~ m - ~ ; Cu-Ka radiation (h = 1.5418 A); p = 64.6 cm-';Philips PW 1100/20 diffractometer; 8-20 scan method. A total of 321 1unique data were collected of which 2221 with I > 30(I) were refined.The structure was solved by the heavy-atom method and refinedanisotropically by a full-matrix procedure; R = 0.058.M + ) .14.021(2), b = 14.846(2), c = 16.504(2); U = 3435.4(7) A3; Z = 41752 J.CHEM. SOC. DALTON TRANS. 19925:*T ASPhI6Fig. 2 An ORTEP plot of the cation of complex 6 with key atomsnumbered. Hydrogen atoms have been omitted for clarity. Selectedinteratomic distances, angles and torsion angles are Fe-As 2.326(2),1.55(2) and C(2)-C(3) 1.52(2) A; Fe-As-C(4) 113.5(4), Fe-As-C(l)129.9(4), Fe-As-C(3) 13 1.4(4), As-C( 1 )-C(2) 91.0(9), C( 1 )-C(2)-C(3)100( l), As-C(3)-C(2) 90.8(9) and C( l)-As-C(3) 72.5(6)"; C(3)-As-- 20( 1) and C( l)-C(2)-C(3)-As 20( 1)"As-C(4) 1.953( 12), As-C( 1) 1.974( 13), As-C(3) 2.004( 12), C( l)-C(2)C(l)-C(2) 15.6(8), C( l)-As-C(3)-C(2) - 15.9(8), As-C(I)-C(~)-C(~)Fig.1 An ORTEP plot of cation A of the complex 4*0.75C6H,*0.25CHC1, with key atoms numbered. Hydrogen atoms have beenomitted for clarity. Selected interatomic distances, angles and torsionangles (and the corresponding values of cation B) are Fe-P(l) 2.193(7)P(l)-C(3) 1.87(2) [1.90(2)], C(l)-C(2) 1.49(3) [1.60(3)] and C(2)-C(3)1.58(3) [1.51(4)] A; Fe-P(lFC(4) 115.3(6) [115.6(8)], Fe-P(1)-C(1)128.3(8) [128.9(6)], Fe-P(lE(3) 124.6(8) [124.8(8)], P(l)-C(l)-C(2)92( 1 ) [90( 1 )I, C( 1 )-C(2)-C(3) W 2 ) C98(2)1, P(1 )-C(3)-W) 89( 1)[91(1)] andC(l)-P(l)-C(3)77.6(8) [77(l)]";C(3)-P(l)-C(l)-C(2) 12(2)[15(l)l, C(1)-P(1)-C(3)-C(2) - 1 l(1) [- 16(1)1, P(1>-C(1)-CWC(3)- 14(2) [ - 19(2)] and C(l)-C(2)-C(3)-P(l) 14(2) [18(2)]"[2.184(6)], P(l)-C(4) 1.88(2) [1.87(2)], P(1)-C(l) 1.85(2) [1.86(3)],data agree well with those calculated for phosphetane(HPCH,CH,CH,)9 and with those determined for variousring-substituted phosphetane oxides and phosphetaniumsalts." To our knowledge, compound 6 is the first arsetanecomplex to be isolated, and there are no other structural dataavailable on the arsacyclobutane ring.Notably, however,substituted phospha- and arsa-cyclobutenes have recently beenisolated and structurally characterized.' The As-C and C-Cdistances within the four-membered ring of complex 6 aretypical of single bonds. The Fe-As bond is elongated withrespect to the sum of the covalent radii (2.28 A), but is almostidentical to that in [Fe(q-C,H,)(CO),(AsPh,)lCBF,I.'We are presently seeking methods of displacement of thefour-membered heterocycles from complexes 4 and 6 andrelated complexes in order to investigate cyclooligomerizationreactions of the monomers under metal-template conditions.-References1 K.Meier and G. Rihs, Angew. Chem., Int. Ed. Engl., 1985, 24, 858;T. I. Kostenko, V. S. Lebedev, I. A. Vakhtina, N. P. Samoilova andM. Ya. Botnikov, J. Org. Chem. USSR (Engl. Transl.), 1988, 24,500; P. G. Jones, T. Gries, H. Griitzmacher, H. W. 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Crystallogr.Spectrosc. Res., 1989,19, 1033.Received 2 lsl January 1992; Communication 2/00333
ISSN:1477-9226
DOI:10.1039/DT9920001751
出版商:RSC
年代:1992
数据来源: RSC