Modelling of Hexacoordinated Transition States of Germanium Based on the Crystal Structures of Germanium-substituted Bis(lactamo-N-methyl)germanes L2GeX2 and L2GeXY (X, Y = Hal, OTf, BF4, l3)

Ovchinnikov, Yuri E.; Struchkov, Yurii T.; Шипов, А. Г.; Smirnova, L. S.; Baukov, Yuri I.; Bylikin, S. Yu.

doi:10.1070/mc1994v004n05abeh000403

Cited by 11 publications

(7 citation statements)

References 7 publications

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“…-UCI x x 2a--r 3a--c (2) The yields of the final products in reaction (2) (76--98%) were higher than those obtained in reaction (1). Taking into account that N-(chloromethyl)lactams are more readily available than the corresponding bromides and iodides and the fact that reaction (2) affords dihalides in higher yields, this reaction is a preferential procedure for the preparative synthesis of the compounds under consideration.…”

Section: Uxcontrasting

confidence: 56%

“…The atomic coordinates in the structures of 2a.h.c and 3a,h are given in Table 9. The principal (14) 4236 (4) 5014 (6) Sn (1) 7522(1) I017(I) 6338(1) C (5) 548 (11) 3791 (4) 5038(4) Br(l) 6740(I) 3913 (2) 5969 (2) C (6) 1038 (11) 3096 (4) 5536(4) Br (2) 9004 (1) 2198 (3) 7389 (2) C (7) 1795 (9) 2546 (3) 4958 (3) O (1) 8047 (9) -1629 (14) 6469 (10) C (8) -1221 (9) 895(3) 3312r O (2) 6235 (8) -354 (17) 5623 (9) C ( (2) 6364 (10) -831 (19) 7519 (11) C(II) 318 (12) -1372 (3) 3011(4) C (I) 7896 (14) 681 (24) 4694 (15) C (12) 2332 (12) -1074(4) 3521(5) C (2) 8865 (14) -1351 (24) 3915 (15) C (13) 2074 (10) -641 (3) 4351(4) C (3) 9350 (17) -3038 (29) 4452 …”

Section: Methodsunclassified

“…Taking into account that N-(chloromethyl)lactams are more readily available than the corresponding bromides and iodides and the fact that reaction (2) affords dihalides in higher yields, this reaction is a preferential procedure for the preparative synthesis of the compounds under consideration. The formation of diiodies 3a--c in reaction (2) was rather unexpected because the reactions of Ge analogs of compounds la--e, viz., dichlorides [L(mI,GeCI2 . with iodine-containing nucleophiles resulted in the replacement of only one C1 atom and only mixed chlorideiodides [L(ml2Ge(CI)i were isolated) This difference is apparently associated with the nature of the central atom in the compounds under study.…”

Section: Uxmentioning

confidence: 98%

“…(1) X = CI (1), Br (2), or I (3); n = 1 (a), 2 (b), or 3 (c) Like dichlorides la--e, compounds 2a and 3a were formed under rather mild conditions (refluxing of a mixture of the reagents in toluene for 2 h) and the target products were obtained in moderate yields (59 and 55%, respectively).…”

Section: A--c 2a--e 3a--cmentioning

confidence: 99%

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Synthesis and crystal and molecular structures of six-coordinate tin dibromides and diiodides containing lactamomethyl C,O-chelating ligands

et al. 1999

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New (O--Sn)-bischelate bis(lactamomethyl)dibromo-and -diiodostannanes [L(n)I2SnX 2 (L is the bidentate lactamomethyt C,O-chelating ligand: n is the size of the lactam ring, 5--7; X = Br or 1) were prepared both by the direct method from metallic tin and the corresponding N-(halomethyl)lactams and by the reactions of dichlorides [k(n)]2SnCI 2 with lithium halides. According to the data of X-ray diffraction analysis, the tin atom in {L(n)I2SnBr2 (n = 5--7) and [L(nqzSnl2 (n = 5 or 6) adopts an octahedral configuration with the carbon atoms in trans positions and the coordinating oxygen and halogen atoms in cispositions with respect to each other. A comparison with the structures of analogous lactamomethyl halide derivatives of Give-and six-coordinate Si, Ge. and Sn demonstrates that the spatial structures of the hypetwalent fragments containing six-coordinate atoms are less sensitive to the replacement of the halide ligands and the central atom. The covalence of the M--Hal bond increases and the covalence of the M--O bond decreases in the series M = Si, Ge, and Sn.Key words: six-coordinate tin compounds, synthesis, multinuclear N MR spectroscopy. X-ray diffraction study.Recentl3/~ we l~ave perforrfled sy~femati~ StudiesO1 s-ix= coordinate silicon, germanium, and tin compounds containing the amidomethyl and related C,O-chelating ligands. !-4 These studies were an extension of investigations of analogous five-coordinate silicon 5,6 and germanium 7,8 derivatives. One of the major lines of investigation of the characteristic features of these compounds involves the elucidation of the properties of three-center hypervalent X--:M::Y-bonds, where-Mis an atom with-an increased coordination number (Si, Ge, or Sn) and X and Y are electronegative atoms or groups (N--C=O, Hal, OTf, etc.).Investigations of tin derivatives as compounds containing six-coordinate atoms allow one to reveal the effects of the involvement of the M atom simultaneously in two hypervalent bonds and to follow the dependence of the properties of these bonds in the series M = Si, Ge, and Sn.

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Section: Uxcontrasting

confidence: 56%

Section: Methodsunclassified

Section: Uxmentioning

confidence: 98%

Section: A--c 2a--e 3a--cmentioning

confidence: 99%

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Synthesis and crystal and molecular structures of six-coordinate tin dibromides and diiodides containing lactamomethyl C,O-chelating ligands

et al. 1999

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“…The extent of deviation of the OMC 3 Cl moiety from TBP toward tetrahedral geometry may also be defined by a single parameter DX = 2p À X, where X is the solid angle 1 formed by three equatorial bonds of the M atom [18]. Instead of standard sr or msr (= 10 À3 sr) units for X, we use more convenient (although non-standard) degree units (°) defined as 360°= 2p sr.…”

Section: X-ray Structural Analysis Of 3bmentioning

confidence: 99%

Reaction of N-trimethylsilyl derivatives of amides and lactams with chloro(chloromethyl)dimethylstannane: Crystal and molecular structure of 1-(chlorodimethylstannylmethyl)-2-piperidone

Bylikin

Шипов

Negrebetsky

et al. 2006

Journal of Organometallic Chemistry

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Hypervalent Compounds of Organic Germanium, Tin and Lead Derivatives

Baukov

Tandura

2009

Patai's Chemistry of Functional Groups

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Introduction and Outline Self‐Associates Pentacoordinate Anionic Compounds Pentacoordinate Intermolecular Neutral Compounds Pentacoordinate Intramolecular Neutral Germanium Compounds Pentacoordinate Intramolecular Neutral Tin and Lead Compounds Pentacoordinate Cationic Compounds Hexacoordinate Anionic Compounds Hexacoordinate Neutral Compounds Hexacoordinate Cationic Tin Compounds Acknowledgments

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Modelling of Hexacoordinated Transition States of Germanium Based on the Crystal Structures of Germanium-substituted Bis(lactamo-N-methyl)germanes L2GeX2 and L2GeXY (X, Y = Hal, OTf, BF4, l3)

Cited by 11 publications

References 7 publications

Synthesis and crystal and molecular structures of six-coordinate tin dibromides and diiodides containing lactamomethyl C,O-chelating ligands

Synthesis and crystal and molecular structures of six-coordinate tin dibromides and diiodides containing lactamomethyl C,O-chelating ligands

Reaction of N-trimethylsilyl derivatives of amides and lactams with chloro(chloromethyl)dimethylstannane: Crystal and molecular structure of 1-(chlorodimethylstannylmethyl)-2-piperidone

Hypervalent Compounds of Organic Germanium, Tin and Lead Derivatives

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