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Bezout's Theorem and ideals of terminal forms

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Inorganica Chimica Acta, 169 (1990) 19-21 19

Inorganica

Chimica

Acta

Oxidations of N,N’-Disubstituted o-Phenylenediamine in the Presence of Metal Ions and the Crystal Structure of N,N’-Dimethylbenzimidazolium Perchlorate, Pyridine-bis(o-benzosemiquinonedi- imine)cobalt(III) Chloride and Bis(pyridine)(N,N’- bistoluene-p-sulfonyl+phenylenediiminato)-

copper

PAI-HSIU CHENG, HEI-Y ING CHENG, CHENGCHEN LIN and SHIE-MING PENG*

Department of Chemistry, National Taiwan University, Taipei 10764 (Taiwan)

(Received December 6,1989)

In continuing research on the metal complexes of o-benzoquinodiimine [l-4], we report the reactions of N,N’-disubstituteda-phenylenediamine with metal ions under basic conditions, and the crystal structure of their products: Arfl’-dimethylbenzimidazolium perchlorate, pyridine-bis(o-benzosemiquinonedi- irnine)cobalt(IlI) chloride, and bis(pyridine)(N,N’- bistoluene-p-sulfonylo-phenylenediiminato)copper-

(II). The diamine molecules (1) can serve as bidentate or monodentate ligands [5]. They can be deproto-

*Author to whom correspondence should be addressed.

-2H’ F3 C_ _e Ej R N,N’disubstituted o-phenylenediamine (OPda) 1 la, R = H lb, R = CH3 lc, R = -C //* ‘@ Id, R = -S-to1 II 0 N,N’disubstituted o-phenylenediiminate (opdi) 2 2a, R = H 2b, R = CH3 2c, R = -C //* ‘9 2d, R = -!-to1 II 0

nated to form dianions (2) and may be further oxidized to form anionic radicals (3) and neutral diimine molecules (4). Compound 3a forms dia- magnetic square-planar complexes with d8 metal ions and 4a forms tris-cu-diimine complexes with d6 metal ions.

The reactions of lb NJ’-dimethyl-o-phenylene- diamine with M(C104)2 (M = Fe(H), Co(H), Ni(II), Cu(I1)) in ethanol result in precipitates of various colours. Purification of these solids led to red crystals of NjV’-dimethylbenzimidazolium perchlorate. The benzimidazole is believed to form by the ring closure of NJ’-dimethyl+phenylenediamine with form- aldehyde, which comes from the oxidative cleavage of the N-methyl group.

CH3 CH3 M (CIO,), lb * HCHO e QcI 9 Cl04 CH3 lb

The red crystals consist of N,N’-dimethylbenz- imidazolium cations and perchlorate anions. The structure of the cation is shown in Fig. 1. The N 1 -C 1 and N2-C2 bonds are short (1.31 a) and exhibit partial double-bond character. The bond pattern is consistent with the proposed structure.

a

NH N,‘or Co’ -HCI - NH PY N,N’disubstituted obenzosemiquinonediimine (s-bqdi) 3 3a, R = H 3b, R = CH3 3c, R = -C,B @ 3d, R = -S-to1 II 0 R G R N,N’disubstituted o-benzoquinonediimine (bqdi) 4 4a, R = H 4b, R = CH3 4c, R = -C //* ‘0

R

4d, R = -S-to1 II 0

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20

Fig. 1. ORTEP drawing of the Nfl’dimethylbenzimidazol- ium cation with 30% probability. Space group, C2/c; formula, (C9HrrNz)+ClOQ: (I = 10.491(6), b = 16.201(3), c= 13.625(26) A; p= 106.2(l)‘, Z= 8. A total of 1218 reflections were observed with I > 20(I), 145 parameters, to give R = 5.6, R, = 6.5%.

10

C 9

c5 C8

Fig. 2. ORTEP drawing of the cation [Co”‘(s-bqdi)zpy]+ with 50% probability. Space group, Q/c; formula, [Co- (CsH,N,),(C,H,N)]+Cl-: a = 14.501(3), b = 12.774(4), c = 18.875(5)A; p = 93.98(2)“, 2 = 8. A total of 1024 reflections were observed with I > 200, 370 parameters, to give R =

3.4, R, = 2.8%. Other pertinent bond parameters: Co-N5, 1.982(7) A; Nl-Co-C5, 98.7(3); N2-Co-N5, 101.2(3); N3-Co-N5, 101.4(3); N4-Co-N5, 97.3(3); Nl-Co-N2, 82.0(3); Nl-Co-N3, 159.8(3); Nl-Co-N4, 95.4(3); N2- Co-N3, 94.1(3); N2-Co-N4, 161.5(3); N3-Co-N4, 82.0(3)“.

The reactions of lc (N,N’-dibenzylu-phenylene- diamine) with metal ions in pyridine resulted in hydrolysis of the amides and led to the isolation of the o-benzosemiquinonediimine metal complexes 3a, e.g. [Ni@)(s-bqdi),] and [Co(m)(s-bqdi),py)]+.

For the crystal structure analysis of [Cocrm(py)- (s-bqdi)Z]+C1-, suitable single crystals were obtained by direct cooling of the reaction mixture of the hydrochloride salt of lc in hot pyridine with CO(OAC)~. The result is shown in Fig. 2. The deep red-purple crystals consist of well-separated pyridine-bis(o-benzosemiquinonediimine)cobalt(III)

cations and chloride anions. The cobalt atom is penta-coordinated in a square-pyramidal geometry with the nitrogen atom of pyridine in the axial site

and four nitrogen atoms of the two a-benzosemi- quinonediimine ligands in the equatorial plane, and

Fig. 3. ORTEP drawing of the molecule bis(pyridine)(N,N’- bistoluenepsulfonyl-o-phenylenediiminatocopper(II),

[Cu@y)z@-toslopdi)], with 50% probability. Space group, C2/c: a = 16.894(2), b = 11.662(2), c = 14.753(4) A; p=

100.62(2)“, Z = 4. A total of 1599 reflections were observed with I > 20(Z), 242 parameters, to give R = 3.5, R,= 2.5%. Pertinent bond parameters: CU-NI, 1.942(3); Cu-N2,

1.998(3); Nl-S, 1.602(3); Nl-C7, 1.399(5); S-01, 1.442(3); S-02, 1.439(3); S-Cl, 1.765(4); C7-C7’, 1.403(7); C7-C8, 1.380(6); C8-C9, 1.372(7); C9-C9’, 1.367(10) A; Nl-Cu-Nl’, 81.0(l); Nl-Cu-N2, 128.8(l); Nl-Cu-N2’, 111.3(l); N2-Cu-N2’, 98.7(l); Cu-Nl-S,

117.5(2); Cu-Nl-C7, 115.9(2); S-N1 -C7, 124.9(3)‘. IM(Py)z@-toslopdi)l complexes with M = Co(H), Ni(l1) or Cu(II) are all isomorphous.

is displaced by 0.314(4) A from the least-squares plane of the four basal nitrogen atoms. The average Co-N distance and bond pattern of the o-benzosemi- quinonediimine ligand in this complex are com- parable to those in similar complexes, e.g. [Mn(s- bqdi)a], (M = Ni [6], Pd*, Pt*, Co [l]) and [ComX- (s-bqdi)Z]+T (X = Cl, Y = none [ I] ; X = opda, Y =

B#4C [71X

The reaction of Id (N,N’-bistoluene-p-sulfonyl- o-phenylenediamine) with metal ions (M = Co(II), Ni(II), Cu(I1)) in pyridine led to the isolation of the o-phenylenediiminate metal complexes 2d [M(R,opdi)(py),] (M = Co(II), Ni(II), Cu(I1); R = S02C6H4CHs). W-Vis spectroscopic data are: for Co(II), 588 nm (e = 6.30 X lo2 M-’ cm-‘), 576 (6.34 X IO*), 520 (5.19 X lo’), 386 (1.68 X 103), 306 (5.76 X 103); for Ni(II), 506 (1.23 X 102), 418 (2.22 X 102), 308 (4.79 X 103); for Cu(II), 820 (broad, 1.51 X 103), 526 (4.42 X lo*), 312 (3.98 X 103).

The result of the X-ray structural analysis of [Cu(RZopdi)(py)z], shown in Fig. 3, indicates that the central copper ion has a distorted tetrahedral coordination. The dihedral angle between the Nl- Cu-Nl’ and N2-Cu-N2’ planes is 74.46(14)‘. The small Cu-NI distance (1.942(3) A) is attributed to

*For [M*r(s-bqdi)?] with M = Pd, Pt. They are isomor- phous with the Ni analogue (ref. 6) (unpublished result).

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21 the negative charge of the nitrogen atom. The large References

C7-Nl distance (1.399(‘S) A) and aromatic bond

lengths in the C7-C8-C9-C9’-C8’-C7’ ring are 1 consistent with the phenylenediiminate structure.

This is the first report of the structure of a dianionic 2

form of this series. 3

4

Acknowledgement 5

6

S. Peng, C. Chen, D. Liaw, C. Chen and Y. Wang, Znorg, Chim. Acta, 101 (1985) L31.

S. Peng, K. Peters and A. Simon, Znorg. Chim. Acta, 101 (1985) L35.

D. Liaw and S. Peng,Znorg. Chim. Acta, 113 (1986) Lll. M. Hsieh, M. Cheng and S. Peng, Inorg. Chim. Acta, 145 (1988) 1.

R. C. Elder, D. Koran and H. B. Mark, Jr., Inorg. Chem., I3 (1974) 1644.

G. S. Hall and R. H. Soderberg, Inorg. Chem., 7 (1968) 2300.

This work was supported by the National Science I M. Zehnder and H. LGllige, Helv. Chim. Acta, 63 (1980)

數據

Fig.  1.  ORTEP  drawing  of  the  Nfl’dimethylbenzimidazol-  ium  cation  with  30%  probability

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