Transition Met. Chem. 7, 41-44 (1982)

Hydrazine complexes with oxocations

41

Complexes of Hydrazine and Substituted Hydrazines with some Oxocations* Anant K. Srivastava**, Ram K. Agarwai***, Mahesh Srivastava, (Miss) Veena Kapur, (Mrs.) Sunita Sharma and Prakash C. Jain** Department of Chemistry, Meerut College, Meerut-250001, India. Summary Several new polymeric complexes of general composition MOn(L)4X2 (where M = V, Zr and U; n = 1 or 2; X = C1, Br, I, NO3 and NCS and L = N2H4, PhNHNH2 and MezNNH2 have been synthesised and characterized by elemental and d.t. analyses and by magnetic measurements, electronic and i.r. spectra. The vanadyl(IV) complexes exhibit subnormal magnetic moments (1.26-1.36BM) possibly because of ex change interaction between vanadium(IV) ions. The thermal stability of hydrazine complexes fall in the order: Cl > Br > NCS > I. The M - N bond strength, as revealed, by v(M-N), decreases as: Me2NNH2 > NzH4 > PhNHNH2. Introduction Although more than sixty oxocation species are known, the complexes of only a few: e.g., VO Iv, ZrO Iv and UO2vr have been extensively investigated. The dioxouranium(VI) complexes are interesting, because a coordination number exceeding six may normally be expected for this ion and the oxovanadium(IV) is known to form either anionic, cationic or even neutral complexes. Hydrazine and substituted hydrazine complexes of oxocations have not been previously investigated. The coordination chemistry of hydrazine and substituted hydrazines is of special interest because of the variety of ways in which these species can be bonded to metal ion: e.g., as unidentate, bidentate or bridging (~-3). In continuation to our investigation (4-7) on complexes of hydrazine and its substituted derivatives, we report herein complexes of VO Iv, ZrO Iv and U O vI with hydrazine (hy), phenylhydrazine (Phhy) and 1,1dimethylhydrazine (1,1-Me2hy). Results and Discussion MOnX2 (where M = V, Zr and U; n = 1 or 2 and X = C1, Br, I, NO3 or NCS) reacts with hydrazines in ethanol to yield complexes of general composition MOnL4X 2 (where L = hy, Phhy and 1,1-Me2hy). The vanadyl complexes of hydrazine alone have one molecule of water of crystallization and the zirconyl and uranyl complexes are hygroscopic. All the complexes are insoluble in most common organic solvents and are fairly stable, except those of Phhy which decompose slowly to yield a product of indefinite composition. As expected, the dioxouranium and oxozirconium complexes are diamagnetic. Recently there has been considerable interest in the synthesis and magnetic properties of oxovanadium complexes with subnormal magnetic moments (s-14) i.e. in the 1.26-1.36 BM

* Presented in symposium on Frontiers of coordination chemistry, Allahabad University, Allahabad, Dec.. 6-8, 1979. ** Authors to whom all correspondence should be directed *** Chemistry Department, L. R. College, Sahibabad (Ghaziabad). 9 Verlag Chemic GmbH, D-6940 Weinheim, 1982

range. These moments are much lower than the spin-only value (1.73 BM) for a d 1 system and are ascribed to an exchange interaction between vanadium(IV) ions. It appears that the complexes are probably polynuclear (9-14). The oxovanadium complexes probably consist of pentacoordinated molecules (15-17) and in the absence of steric hindrance, are expected to be square pyramidal with four hydrazines, most probably in a planar arrangement 06~, as is evident from the electronic spectra which are in agreement with the data reported for similar complexes (16). Of the three main bands, designated I, II and III, the first two are not well developed and appear only as shoulders. A controversy (15' ~8~ exists regarding the spectral band assignments of oxovanadium complexes. According to the V - M scheme (19b), the first shoulder, centred at ca. 13 000 cm -1, has been assigned to an unresolved band resulting from a dxy---~dyz; dxz transition. The second shoulder in the 15 000-17 000 cm- region, is attributed to the dxy---~dx2_y2transition and the third well developed band to the dxy~ dz2 transition. I.r. spectra

Table 3 records partial i.r. spectral data and the proposed assignment of the observed frequencies of the complexes of hydrazine and substituted hydrazines. Two bands observed in the 3000 cm -1 region in the i.r. spectra are obviously due to NH2 stretching vibrations and are at lower frequency than the bands for gaseous hydrazine (21). This N - H band weakening results from the electron withdrawal from nitrogen upon coordination to the metal. The band at ca. 1600 cm -1 can be assigned to the NH2 wagging and twisting vibrations. The N - N stretching vibration decides the mode of coordination of hydrazines. This vibration occurs at ca. 930 cm -1 when hydrazine acts as unidentate while in complexes containing bidentate bridging hydrazine, v(N-N) is found at ca. 970 cm -1(22). A perusal of Table 3 reveals that all the reported complexes contain chelated hydrazines or perhaps more likely, in view of their insolubility and thermal stability, a polymeric network containing bridging hydrazines. All complexes show two bands in the 700-500 cm -1 region, the one at higher frequency (ca. 700 cm -1) being assigned to the asymmetric rocking of the NH2 group and the other, at lower frequency, to the symmetric NH2 rocking mode. v(M-N), observed in the 460-370 cm -1 region, is comparable to bands reported earlier (23-25). The characteristic v ( M = O ) band occurs at 980 _ 40 cm-1. (26' 27) The pseudohalide ion, SCN-, is known to form complexes through its hard (N) or the soft (S) - terminus, or to behave as a bridging ligand (2s). The three observed frequencies at ca. 2120-2080 cm -1, 720-690 cm -a, and 470-410 cm -~ in the zirconyl and uranyl ion complexes fall within the range proposed for N-bonded NCS and are assigned as C-N stretch (v0, C-S stretch (v3) and N - C - S bending (v2) respectively. The presence of ionic nitrate in zirconyl and uranyl complexes is supported by the presence of two bands at ca. 1360 0340--4285/82/0102-0041502.50/0

42 Table

A.K. Srivastava, R. K. Agarwal, M. Srivastava, V. Kapur, S. Sharma and P. C. Jain 1.

Analytical

data

and

magnetic

Compound

moments

of hydrazine,

phenylhydrazine

Found(Calcd) % M

VO(N2H4)4CI2. H20 VO(N2H4)4Br2. H20 VO(N2H4)412. H20 ZrO(N2H4)4.02 ZrO(N2H4)4. at2 ZrO(N2H4)4 9 I2 ZrO(N2I-L)4(NCS)2 ZrO(N2H4)4(NO3)2 UO2(NEH4)4CI2 UO2(N2H4)4Br2 UO2(N2H4)412 UO2(N2H4)4(NCS)2 UO2(N2H4)4(NO3)2 VO(C6I-IsNHNH2)4CI2 VO(C6HsNHNH2)4Br2 VO(C6HsNHNH2)412 ZrO(C6HsNHNH274C12 Z rO(C6HsNHNH2)4Br2 ZrO(C6HsNHNH2),I2 ZrO(C6HsNHNH2)4(NCS)2 ZrO(C6I-IsNHNH2),(NO3)2 UO2(C6HsNHNH2)4C12 UO2(C6HsNHNH2),Br2 UO2(C6HsNHNHz)412 UO2(C6HsNHNH2)4(NCS)2 U O z ( C 6 H 5 N H N H 2 ) 4 ( N O 3 )2

VO(Me2NNH2)4C12 VO(Me2NNH2)4Br2 VO(Me2NNH2)412 ZrO(Me2NNH2)4C12 ZrO(Me2NNH2)4Br2 ZrO(Me2NNH2)412 ZrO(Me2NNH2)4(NCS)2 ZrO(Me2NNH2)4(NO3)2 UO2(MezNNH2)4CI2 UO2(Me2NNH2)4Br2 UO2(Me2NNH2)412 UO2(Me2NNH2)4(NCS)2 UOe(Me2NNHz)4(NO3)2

2. Electronic spectral data of oxovanadium(IV) complexes (cm-1). Compound

dxy--*dyz, dxz

dxy--~d~a_y

d.y--* d:

VO(N2H4)4CI2 9 1-120 VO(N2H4)4Br2 9 1420 VO(N2H4)aIz 9 H20 VO(C6I-IsNHNH2)4C12 VO(Cd-IsNHNH2)4Br2 VO(C6HsNHNH2)412 VO(Me2NNH2)4C12 VO(MezNNH2)4Br2 VO(MezNNH2)A2

12500sh 12550sh 12820sh 12150sh 12050sh 12000sh 12800sh 13120sh -

15150sh 15150sh 17240sh 15000sh 15120sh 15800sh 15920sh 15750sh

20830 21740 22730 20500 20100 20000 22500 22780 22890

Thermal

+

V4)(31) combi-

behaviour

The thermal behaviour of hydrazine complexes has been investigated to a limited extent (3~ and has been extended to the hydrazine oxocation complexes in the present studies.

7,

41-44 (1982)

complexes.

Anion

41.8(41.8) 31.3(31.4) 24.8(24.8) 38.1(38.2) 29.4(29.5) 23.6(23.7) 41.7(41.8) 40.9(40.8) 23.6(23.7) 20.0(20.1) 17.3(17.2) 27.4(27.2) 26.7 (26.8) 19.8(19.9) 17.0(17.2) 14.9(15.0) 18.3(18.6) 15.9(16.1) 14.4(14.3) 21.6(21.6) 21.4(21.4) 14.8(14.6) 13.0(13.1) 11.7(11.8) 17.1(17.3) 17.2(17.1) 29.4(29.6) 23.8(24.0) 20.1(20.0) 26.6(26.8) 22.0(22.1) 18.5(18.6) 30.3(30.2) 29.8(29.7) 19.4(19.3) 16.8(16.7) 14.5(14.7) 22.6(22.4) 22.1(22.1)

Table

and 830 cm -1 and due to the absence of the (vl nation mode in the 1800--1700 cm -1 region.

and 1,1-dimethylhydrazine

N

18.2(17.95) 13.3(13.7) 10.7(10.9) 30.0(29.8) 24.0(23.0) 18.3(18.6) 28.2(28.6) 25.5(25.4) 50.4(50.7) 42.2(42.65) 37.0(36.5) 52.7(52.9) 45.6 (45.6) 9.0(9.1) 7.5(7.8) 6.6(6.8) 15.1(15.1) 13.0(13.1 11.5(11.6) 14.2(14.1) 13.8(13.9) 31.0(31.1) 27.5(27.9) 20.9(20.1) 29.1(29.4) 28.9(29.1) 13.4(13.5) 10.8(10.9) 8.9(9.0) 21.9(21.8) 17.7(18.0) 15.3(15.2) 19.8(19.7) 19.4(19.35) 40.8(41.0) 35.6(35.5) 31.3(31.15) 37.9(38.0) 37.6(37.5)

Transition Met. Chem.

24.8(25.0) 43.0(42.9) 54.0(54.4) 23.0(23.2) 40.8(40.5) 51.7(51.9) 15.1 (15.2) 28.2(28.7) 39.15(38.9) 12.5(12.6) 24.4(24.6) 34.2(34.17) 11.5(11.8) 23.3(23.1) 32.5(32.3) 9.2(9.3) 18.5(18.7) 26.5(26.8) 18.9(18.8) 34.4(34.3) 45.1(45.3) 16.8(17.0) 31.4(31.5) 42.2(42.2) 12.3(12.2) 23.8(23.9) 33.1(33.2) -

I&ff (BM) 1.26 1.36 1.30 Diamag. Diamag. Diamag. Diamag. Diamag. Diamag. Diamag. Diamag. Diamag. Diamag. 1.28 1.30 1.32 Diamag. Diamag. Diamag. Diamag. Diamag. Diamag. Diamag. Diamag. Diamag. Diamag. 1.33 1.29 1.34 Diamag. Diamag. Diamag. Diamag. Diamag Diamag. Diamag. Diamag. Diamag. Diamag.

The thermograms of chloride, bromide and iodo oxovanadium(IV) complexes exhibit a small exothermic peak at c a . 110 ~ due to the presence of a water molecule in these complexes. These complexes decompose exothermically at 300 ~ 280 ~ and 270 ~ respectively. At this stage all the ligand molecules are lost and the end product, in all the cases, is V205 (endo peak, c a . 500 ~ preceded by an intermediate product, V O 2.

D.t.a's of some dioxouranium(VI) complexes of hydrazine have already been recorded and studied by Athavale e t ai.(32). The end product in all the complexes described herein is U308 (endo peak, c a . 820~ The thermograms of the oxozirconium(IV) complexes are identical as regards their major details. All the complexes exhibit an exo peak at c a . 70 ~ owing to their hygroscopic nature. The chloro, bromo and iodo complexes decompose endothermically at 240 ~ 230 ~ 180 ~ respectively, whereas the thiocyanato complex decomposes exothermically at 210 ~ The ultimate product in each case is ZrO 2 (exo peak at ca. 500~ Thus, thermal stability of oxocation complexes falls in the order: C1 > Br > NCS > I.

Hydrazine complexes with oxocations

Transition Met. Chem. 7, 41-44 (1982)

43

Table 3. Partial (a) i.r. spectral bands (cm -1) of oxocations complexes of hydrazine, phenylhydrazine and 1,1-dimethylhydrazine. Complex

v(NH2) or v(NH)

6(NH2)

v(N-N)

v(M=O)

v(M-N)

VO(hy)4Cl2 " H20 VO(hy)4Br: 9 H20 VO(hy)412 9 H20 ZrO(hy)4(NO3)2 ZrO(hy)4C12 ZrO(hy)4Br2 ZrO(hy)j2 ZrO(hy)4(NCS)2 UO2(hy)4(NO3)2 UO2(hy)4Cl~ UO2(hy)4Br2 UO2(hy)412 UO:(hy)4(NCS)2 VO(Phhy)4C12 VO(Phhy)4Br2 VO(Phhy)412 ZrO(Phhy)4C12 ZrO(Phhy)4Br2 ZrO(Phhy)J2 ZrO(Phhy)4(NCS)2 ZrO(Phhy)4(NO3)2 UO2(Phhy)4C12 UO2(Phhy)4Br2 UO2(Phhy)412 UO2(Phhy)4(NCS)2 UO2(Phhy)4(NO3)2 VO(Me2hy)4CI2 VO(Me2hy)4Br2 VO(Me2hy)412 ZrO(Me2hy)4C12 ZrO(Me2hy) 4Br2 ZrO(Me2hy)412 ZrO(Me2hy)4(NCS)2 ZrO(Me2hy)4(NO3)2 UO2(Me2hy)4CI2 UO2(Me2hy)4Br2 UO2(Me2hy)412 UO2(Me2hy)4(NCS)2 UO2(Me2hy)4(NO3)2

3400sbr 3400sbr 3380sbr 3500s, 3200s 3400s, 3120s 3480s, 3100s 3400s, 3120s 3350s, 3180s 3440sbr, 3240sbr 3500sbr, 3280sbr 3500sbr, 3180sbr 3500sbr, 3440sbr 3380sbr, 3500sbr 3350sbr 3360sbr 3340s, 3210s 3370s, 3090s 3370s 3320s, 3120s 3310s, 3100s 3350sbr 3360sbr 3280s, 3120s 3370sbr 3350sbr, 3180s 3380sbr, 3130s 3350s 3340s 3360sbr 3290s 3270s 3300s 3320s 3280s 3310s 3340s 3350s 3320s 3300s

1620s 1610m 1620m 1640m 1630m 1620m 1630s 1600s 1600s 1610s 1615m 1620m 1620m 1600m 1610m 1600m 1540m 1605s 1620s 1615m 1600m 1595m 1605s 1620s 1600s 1610m 1580m 1590m 1610s 1600s 1605m 1620m 1600s 1615m 1595m 1605s 1600s 1600m 1610s

1000m 985s 980m 960w 980w 970w 980m 985w 980w 985s 985s 975w 990w 960w 980m 960w 980w 970w 965w 960w 960w 960w 965w 995m 975w 980m 970w 980w 1000m 960w 960w 975w 965w 980m 990m

-

420w 415w 415w 425w 420w 400w 420w 410w 425m 420m 415m 415m 420m 410w 415w 370w 390w 400w 400w 410w 380w 415w 380w 405w 395w 390w 430w 440w 455w 435w 425w 445w 445w 460w 435w 440w 445w 450w 445w

990m 1010m 990m 1000m 1000m 1000w 990s 1000m 990m 1000m 1000m 1000m 990m 990m 990m 995m 1010m 1000m 990s 1000m 1000m 990m 1000m 990m 1000s 990m 995m -

Table 4. Thermal behaviour of hydrazine complexes. (i)

VO(hy)4X2 9 H20 Exo peak, 100,~ VO(hy)4X2 Exo peak; -4hy ~ VOX2 --* VO2 50--~ 0~ V:O5 -H~O C1 = 300~ Br = 280~ I = 270~ [O]

(ii)

ZrO(hy)4X2 Exo peak ZrO(hy)4X2 C1 = 240~ Br = 230~ , ZrOX2 Exo peak, ZrO2 50-700 I = 180~ NCS = 210~ -4hy 500~ [O] (X = CI, Br, I or NCS)

(iii)

UO2(hy)4X2

Exo peak C1 = 180~ Br = 1"I0~ I = 150~ Endo peak , UO2(hy)4X2 , UO2X2 ~ U308. 50-80~ NCS = 160~ -4hy 820~ [O]

Experimental

Materials

Isolation of the complexes

NzH4 9 H 2 0 and P h N H N H e ( B D H ) and Me2NNH2 9 HC1 (Fluka), were used as supplied. VOC12 and VOBr2 were prepared from V205 (19a) and V O l e was obtained by treating an E t O H solution of VOC12 with an E t O H solution of KI (e~ D i o x o u r a n i u m and oxozirconium salts were p r e p a r e d from their nitrates.

The complexes were p r e p a r e d by the following general procedure. To a solution of the oxocation salt (0.01 mmole) in anhydrous E t O H was added the respective hydrazine (0.06 m m o l e ) with constant stirring. The c o m p o u n d s which precipitated were filtered, washed several times with small amounts of E t O H and finally with E t 2 0 and dried in vacuo over P4010 .

44

M. Royo, F. Melo, A. Manrique and L. Oro

Transition Met. Chem. 7, 44-49 (1982)

Physical measurements Magnetic susceptibilities Were measured on the powdered form of the complexes on a G o u y ' s balance at room temperature using CuSO4 9 5 H 2 0 as calibrant. The i.r. spectra were recorded on a B e c k m a n n i.r. 20 spectrophotometer in KBr in the 4000-200 cm -~ region. Solid state diffused reflectance spectra and differential thermograms were obtained from G.N. Dev University, Amritsar.

Acknowledgements The authors ( R K A , MS, V K and SS) thank the U . G . C . , New Delhi; C.S.T., Lucknow and CSIR, New Delhi, for financial support. T h a n k s are also due to Prof. S. S. Sandhu for d.t.a, and reflectance spectra.

References (1) j. R. Dilworth, Coord. Chem. Rev., 21, 129 (1976). - (2) L. F. Audreith and B. A. Ogg, The Chemistry of Hydrazine, Wiley, New York, (1951). - (3) M. Akbar All and S. E. Livingstone, Coord. Chem. Rev., 13, 101 (1974). - (4)A. K. Srivastava and F. Tarli, J. lnorg. Nucl. Chem., 39, 1793 (1977). - (s) A. K. Srivastava, P. C. Jain and A. L. Varshney, J. Inorg. Nucl. Chem., 42, 47 (1980). - (61A. K. Srivastava, Croatica Chim. Acta, 52, 293 (1979). - (7) A. K. Srivastava, Transition Met. Chem., 5, 143 (1980). - (8) V. VI Zelentsov, Russ. J. Inorg. Chem., 7, 670 (1962). - (9) A. P. Ginsberg, E. Koubek and H. J. Williams, Inorg. Chem., 5, 1956 (1966). - (10)V. T. Kalinnikov, V. V. Zelentsov, O. N. Kuzmicheva and T. G. Aminov, Russ. J. Inorg. Chem., 15, 341 (1970).

(~) A. T. Casey and J. R. Thackray, Austr. J. Chem., 22, 2549 (1969). _ (12)C. C. Lee, A. Shyamal and L. J. Theriot, Inorg. Chem., 10, 1869 (1971). - (13)S. N. Poddar, K. Dey, J. Haldar and H. S. Nathsankar, J. Indian Chem. Soc., 47, 743 (1970). - (14)y. Kuge and S. Yamada, Bull. Soc. Chem. Jpn., 43, 3972 (1970). - (15)S. Yamada and Y. Kuge, Bull. Chem. Soc. Jpn., 42, 152 (1969). - (16)L. Sacconi and U. Campigli, Inorg. Chem., 5, 606 (1966). - (17)j. Selbin, Coord. Chem. Rev., 1, 293 (1966). - (18)j. Selbin, Chem. Rev., 65, 153 (1965). - (19,)C. N. Sathyanarayana and C. C. Patel, Indian J. Chem., 3, 486 (1965). - (19b) L. G. Vanquickenborne and S. P. McGlynn, Theor. Chim. Acta, 9, 390 (1960). - (20)S. K. Madan and H. H. Denk, J. Inorg. Nucl. Chem., 27, 1049 (1965). (21) p. A. Giguera and T. D. Liu, J. Chem. Phys., 20, 136 (1952). - i22) D. Nicholls, M. Rowley and R. S. Swinetells, J. Chem. Soc., A, 980 (1966). - (~) G. M. Barrow, R. H. Kneger and F. Basolo, J. Inorg. Nucl. Chem., 2, 340 (1956). - (24) F. P. Bertin, I. Nakagawa, 8. Muzushima, J. J. Lane and J. V. Quagliano, J. Am. Chem. Soc., 80, 525 (1958). - (25)K. Nakamoto in A. E. Martell (Ed.), Infrared Spectra in A.C.S. (Monograph No. 168), 1971, p. 167. - (26)S. K. Madan and A. M. Donohne, J. Inorg. Nucl. Chem., 28, 1330 (1966). - (27) C. G. Barraclough, J. Lewis and R. S. Nyholm, J. Chem. Soc., 3552 (1959). _ (28~j. L. Burmeister, Coord. Chem. Rev., 1, 205 (1966); 3, 225 (1968). - (29) C. C. Addison, N. Logan, C. S. Wallwork and C. D. Garner, Quart Rev., 25, 289 (1971). - (3o) N. F. Curtis and Y. M. Curtis, Inorg. Chem., 4, 804 (1968).

(31) A. B. P. Lever, E. Mantiovani and B. S. Ramaswamy, Can. J. Chem., 49, 1957 (1971). - (32) V. T. Athavale and C. S. Padmanabhaiyer, J. Inorg. Nucl. Chem., 29, 1003 (1967).

(Received March 9th, 1981)

T M C 622

Hydroformylation of 1-Heptene by a [Rh(NBD)C1]z/PPh3 System. A Kinetic Approach Miguel Royo*, Francisco Melo and Antonio Manrique Instituto de Catfilisis y Petroleoquimica (C.S.I.C.) Serrano, 119, Madrid-6, Spain.

Luis Oro D e p a r t a m e n t o de Qufmica Inorgfinica, Facultad de Ciencias, Universidad de Zaragoza, Zaragoza, Spain.

Summary A kinetic study of the hydroformylation of 1-heptene by a [Rh(NBD)C1]2/PPh3 system, taking into account possible gasliquid mass-transfer restrictions, is presented. The catalytic activity in different solvents is evaluated. With Me2CO as solvent, the kinetic E q u a t i o n (1) is obtained. Rate = - d C / d t = k' C1/2CRhl/4(pHJPco) 1/2

(1)

The apparent rate constants for the formation of n- and isoaldehydes, and their temperature variation, account for the

* Author to whom all correspondence should be directed. 0340-4285/82/0102-0044502.50/0

selectivity change with temperature. The overall mass-transfer coefficient (kLa) has b e e n evaluated from mass-transfer considerations and rate data.

Introduction Since the work by Wilkinson et al.(1), the hydroformylation of olefins using r h o d i u m complexes as catalysts has been the subject of m a n y papers (2-5). However, some of these contributions lack explanation regarding the possible gas-liquid masstransfer restrictions, which, in some cases, could distort the results due to the usually high activity of this type of rhodium complexes in hydroformylation of olefins and the relatively low solubility of hydrogen in some organic solvents. 9 Verlag Chemie GmbH, D-6940 Weinheim, 1982