Complexes of hypercoordinate germanium with novel five-membered monoanionic (O,O)-chelating ligands based on 2-hydroxycarboxamides

Full text of DOI:10.1007/s11172-006-0104-7

Russian Chemical Bulletin, International Edition, Vol. 54, No. 9, pp. 2233—2234, September, 2005
2233
Letters to the Editor
Complexes of hypercoordinate germanium with
novel fiveꢀmembered monoanionic (O,O)ꢀchelating ligands
based on 2ꢀhydroxycarboxamides*
A. G. Shipov,a E. P. Kramarova,a T. P. Murasheva,a Vad. V. Negrebetsky,a
S. Yu. Bylikin,a A. A. Korlyukov,b and Yu. I. Baukovaꢀ
aRussian State Medical University,
1 ul. Ostrovityanova, 117997 Moscow, Russian Federation.
Fax: +7 (495) 434 0329. Eꢀmail: baukov.rgmu@mtuꢀnet.ru
bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (495) 135 5085. Eꢀmail: alex@xrlab.ineos.ac.ru
Complexes of hypercoordinate germanium with
(O,O)ꢀ and (S,S)ꢀdianionic, (C,O)ꢀ, (O,S)ꢀmonoꢀ and
dianionic, and (O,N)ꢀmonoanionic chelating ligands have
been well studied to date.1 However, only a few germaꢀ
nium complexes containing bidentate (O,O)ꢀmonoꢀ
anionic chelating ligands have been structurally characꢀ
terized. The examples include sixꢀcoordinate
acetylacetonate2a,b and benzohydroximate3 trischelate
complexes, a sixꢀcoordinate bischelate complex with an
amygdalic acid fragment as a ligand,4 and a fiveꢀcoordiꢀ
nate bischelate complex derived from the hydroxy ketone
PhCH(OH)C(=O)Ph.5
This method can be illustrated with a reaction of
trichloro(chloromethyl)germane with N,NꢀdimethylꢀOꢀ
trimethylsilylamygdalamide (1), which yielded neutral
fiveꢀcoordinate monochelate 2 (Scheme 1).
According to the Xꢀray diffraction data, the coordinaꢀ
tion polyhedron of the Ge atom in crystal 2 is a slightly
distorted trigonal bipyramid with the carbonyl O atom
and one of the Cl atoms in the vertices (Fig. 1, Table 1). It
should be noted that the equatorial Ge—Cl bond is
somewhat shorter than analogous bonds in fiveꢀmemꢀ
bered monoꢀ(C,O)ꢀchelate complexes with the fragment
Cl3Ge—C—Y—C=O (Y = C and N).6 The length of the
equatorial Ge—O bond is close to the standard value
(1.78 Å) in tetrahedral germanium complexes.1b The comꢀ
prehensive Xꢀray diffraction data for complex 2 will be
published elsewhere.
We found that reactions of germanium polyhalides
with 2ꢀtrimethylsilyloxycarboxamides can be used as a
general route to novel hypercoordinate germanium comꢀ
plexes containing monoanionic (O,O)ꢀchelating ligands.
Fiveꢀcoordinate complex 2 containing a dichloꢀ
ro(chloromethyl)germyl group is also of interest as a startꢀ
ing reagent for the synthesis of hypercoordinate germaꢀ
* Dedicated to Academician A. L. Buchachenko on the occaꢀ
sion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2164—2165, September, 2005.
1066ꢀ5285/05/5409ꢀ2233 © 2005 Springer Science+Business Media, Inc.

2234
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
Shipov et al.
Scheme 1
(2.28 g, 0.01 mol) was added to a stirred solution of amide 1
(2.51 g, 0.01 mol) in benzene (9 mL). The reaction mixture was
refluxed for 1 h, cooled, and kept at room temperature for 3 days.
Then it was concentrated and hexane (4 mL) was added. The
crystals that formed were filtered off. Recrystallization from
benzene—hexane (4 : 3) gave compound 2 (3.32 g, 89%),
m.p. 98—102 °C. Found (%): C, 35.47; H, 3.81, N, 3.69.
C11H14Cl3GeNO2. Calculated (%): C, 35.59; H, 3.88; N, 3.77.
IR (Specord IRꢀ75, KBr, CH2Cl2), ν/cm–1: 1635 w, 1500
(NCO, Ph). 1H NMR (Varian XLꢀ400, 400.1 MHz, CDCl3), δ:
7.27—7.44 (m, 5 H, Ph); 2.80, 3.20 (both s, 3 H each, NMe2);
5.63 (s, 1 H, CH); 3.78, 3.83 (both dd, 1 H each, CH2Cl,
2JH,H = 11.4 Hz).
Bisꢀ(O→Ge)ꢀchelate N,NꢀdimethylꢀOꢀ[dichloro(2,2ꢀdiꢀ
methylꢀ4ꢀoxobenzo[2H]ꢀ1,3ꢀoxazinꢀ3ꢀylmethyl)germyl]amygdalꢀ
amide (4). A mixture of amide 2 (0.18 g, 0.0005 mol) and comꢀ
pound 3 (0.13 g, 0.0005 mol) was refluxed in toluene (2 mL) for
10 h and then cooled to room temperature. The solvent and
Me3SiCl were removed in a rotary evaporator. The residue was
crystallized by triturating with ether (10 mL). The yield of comꢀ
pound 4 was 0.2 g (80%), m.p. 220—222 °C (benzene—hexꢀ
ane, 14 : 1). Found (%): C, 49.27; H, 4.68; N, 5.37.
C21H24Cl2GeN2O4. Calculated (%): C, 49.27; H, 4.72; N, 5.47.
Cl(1)
O(2)
C(12)
C(13)
Cl(3)
1
IR (CH2Cl2), ν/cm–1: 1607, 1564, 1500 (NCO, Ar). H NMR
C(2)
Ge(1)
Cl(2)
C(11)
(CDCl3), δ: 1.78, 1.80 (both s, 3 H each, CMe2); 2.76, 3.11
(both s, 3 H each, NMe2), 3.78, 3.83 (both dd, 1 H each, CH2,
2JH,H = 11.4 Hz); 7.33—7.47 (m, 5 H, Ph); 5.67 (s, 1 H, CH);
C(3)
C(16)
7.00 (d, 1 H, H(9), 3JH,H = 7.8 Hz); 7.14 (t, 1 H, H(7), 3JH,H
=
C(14)
C(15)
7.8 Hz); 7.57 (t, 1 H, H(8), 3JH,H = 7.8 Hz); 7.92 (d, 1 H, H(6),
3JH,H = 7.8 Hz).
C(1)
O(1)
C(5)
N(1)
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 04ꢀ03ꢀ32557)
and the International Association for the promotion of
cooperation with scientists from the states of the former
Soviet Union (INTAS, Project No. 03ꢀ51ꢀ4164).
C(4)
Fig. 1. Crystal structure of Cl2(CH2Cl)GeOCHPhC(O)NMe2 (2).
Table 1. Selected bond lengths (d) and angles (ω) in structure 2
References
Bond
d/Å
Angle
ω/deg
1. (a) Yu. I. Baukov and S. N. Tandura, in The Chemistry of
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Ed. S. Patai, Wiley, London, 2002, 961; (b) K. M. Mackay,
in The Chemistry of Organic Germanium, Tin and Lead Comꢀ
pounds, Vol. 2, Ed. Z. Rappoport, Wiley, Chichester,
1995, 97.
Ge(1)—O(1) 2.066(2)
Ge(1)—O(2) 1.781(2)
Ge(1)—Cl(1) 2.255(1)
Ge(1)—Cl(2) 2.1184(1)
Ge(1)—C(3) 1.956(3)
Cl(3)—C(3) 1.743(3)
O(1)—Ge(1)—O(2) 82.28(8)
O(1)—Ge(1)—Cl(1) 171.31(6)
Cl(1)—Ge(1)—Cl(2) 95.80(3)
O(1)—Ge(1)—Cl(2) 89.51(6)
2. (a) T. Ito, K.Toriumi, F. B. Ueno, and K. Saito, Acta
Crystallogr., Sect. B, 1980, 36, 2998; (b) P. S. Koroteev,
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nium bischelate complexes by reactions with Nꢀtrimethylꢀ
silyl derivatives of amides and related compounds.7 For
example, the reaction of complex 2 with 2,2ꢀdimethylꢀ3ꢀ
trimethylsilylbenzo[2H ]ꢀ1,3ꢀoxazinꢀ4ꢀone (3) gave bisꢀ
chelate 4 with two different chelating ligands: the amygdalꢀ
amide residue and the 2,2ꢀdimethylꢀ4ꢀoxobenzo[2H ]ꢀ
1,3ꢀoxazinꢀ3ꢀylmethyl (Bon) monoanionic C,Oꢀchelatꢀ
ing ligand (see Scheme 1).
The hexacoordination of germanium in complex 4
was confirmed by Xꢀray diffraction analysis and will be
discussed elsewhere.
(O→Ge)ꢀChelate N,NꢀdimethylꢀOꢀ[dichloro(chloromeꢀ
thyl)germyl]amygdalamide (2). Trichloro(chloromethyl)germane
Received July 6, 2005