Organometallic Aluminum Compounds Derived from 2-(1,3,5-Dithiazinan-5-yl)ethanol Ligands

Article abstract of DOI:10.1021/ic034642+

The reactions of AlMe₂Y (Y = Me or Cl) with new ligands 2-(1,3,5-dithiazinan-5-yl)ethanol (1), 2-(1,3,5-dithiazinan-5-yl)-1-methylethanol (2), and 2-(1,3,5-dithiazinan-5-yl)-1-phenylethanol (3) are described. The ligands are coordinated to aluminum atoms by nitrogen and oxygen atoms, with a nitrogen based spiranic structure. Equimolar reactions gave dimeric structures bearing pentacoordinated aluminum atoms O-(AlMeY)-2-(1,3,5-dithiazinan-5-yl)ethanolates (4-7) as well as monometallic compounds with tetracoordinated aluminum atoms O-(AlMeY)-2-(1,3,5-dithiazinan-5-yl)ethanolates (8-9). Reactions with 2 equiv of the aluminum reagents afforded tetracoordinated dialuminum complexes O-(AlMeY)-O-(AlMe₂Y)-2-(1,3,5-dithiazinan-5-yl)ethanolate (10-18). The structures of the new compounds were determined by NMR (¹H, ¹³C, and ²⁷Al) and complemented by X-ray diffraction of compounds 4, 10, and 16-18. Relevant intermolecular interactions C-H...S, C-H...Cl, and C-H...π found in the crystalline network are reported.

Full text of DOI:10.1021/ic034642+

Inorg. Chem. 2003, 42, 7569−7578
Organometallic Aluminum Compounds Derived from
2-(1,3,5-Dithiazinan-5-yl)ethanol Ligands1
,†
Juan Carlos Ga´lvez-Ruiz,† Henrich No1th,‡ and Angelina Flores-Parra*
Departamento de Qu´ımica, Centro de InVestigacio´n y de Estudios AVanzados del I.P.N.,
A.P. 14-740, C.P. 07000 Me´xico D.F., Me´xico, and Department Chemie,
Ludwig-Maximilians-UniVersita¨t, Butenandt-Strasse 5-13(Haus D), D-81377 Mu¨nchen, Germany
Received June 9, 2003
The reactions of AlMe2Y(Y) Me or Cl) with new ligands 2-(1,3,5-dithiazinan-5-yl)ethanol (1), 2-(1,3,5-dithiazinan-
5-yl)-1-methylethanol (2), and 2-(1,3,5-dithiazinan-5-yl)-1-phenylethanol (3) are described. The ligands are coordinated
to aluminum atoms by nitrogen and oxygen atoms, with a nitrogen based spiranic structure. Equimolar reactions
gave dimeric structures bearing pentacoordinated aluminum atoms O-(AlMeY)-2-(1,3,5-dithiazinan-5-yl)ethanolates
(4−7) as well as monometallic compounds with tetracoordinated aluminum atoms O-(AlMeY)-2-(1,3,5-dithiazinan-
5-yl)ethanolates (8−9). Reactions with 2 equiv of the aluminum reagents afforded tetracoordinated dialuminum
complexes O-(AlMeY)-O-(AlMe Y)-2-(1,3,5-dithiazinan-5-yl)ethanolate (10−18). The structures of the new compounds
2
were determined by NMR (1H,13C, and 27Al) and complemented by X-ray diffraction of compounds 4, 10, and
16−18. Relevant intermolecular interactions C−H‚‚‚S, C−H‚‚‚Cl, and C−H‚‚‚π found in the crystalline network are
reported.
Introduction
solution to the mentioned reagents. 1,3,5-Dithiazinanes are
heterocycles rich in electron pairs; their rings are easily
opened with metal or reducing reagents and, therefore,
scarcely studied. These heterocycles react with Lewis acids
in various ways which depend on the stoichiometry and the
reaction conditions. The borane adducts of the 1,3,5-
dithiazinanes have been prepared and were analyzed by NMR
and X-ray diffraction. Boron hydrides, BH3-nXn, give N-
adducts and borataheterocycles by ring opening reactions.2b,3e
They differ from the boron analogues in their conformational
behavior. Moreover, they crystallize easily. Our results
encouraged us to prepare new 1,3,5-dithiazinanes bearing
an N-ethanol group which not only acts as a chelating arm
also contains an OH group that was expected to form
covalent bonds to aluminum. In particular, our efforts were
focused on investigating the selectivity and stereochemistry
of the coordination reactions with AlMe3 and AlMe2Cl, and
their susceptibility to give monomers oligomers or polymers.
The ligands 2-(1,3,5)-dithiazinan-5-yl-ethanol (1), 2-(1,3,5)-
dithiazinan-5-yl-1-methyl-ethanol (2), and 2-(1,3,5)-di-
thiazinan-5-yl-1-phenyl-ethanol (3) were prepared from
formaldehyde, NaSH, and the corresponding ethanolamines
in good yields as described in Scheme 1.
We are currently investigating the chemistry and the
coordinating ability2,3 of 1,3,5-heterocyclohexanes. The
condensation of formaldehyde and primary amines affords
oxadiazinanes2a or triazinanes;2c whereas thiadiazinanes2b or
dithiazinanes2c,d are obtained by adding an aqueous NaSH
* To whom correspondence should be addressed. E-mail: aflores@
mail.cinvestav.mx. Fax: (555) 57 47 71 13.
† Centro de Investigacio´n y de Estudios Avanzados del I.P.N.
‡ Ludwig-Maximilians-Universita¨t.
(1) This work is part of the Ph.D. thesis of J. C. Ga´lvez-Ruiz, Cinvestav,
Mexico.
(2) (a) Flores-Parra, A.; Sa´nchez-Ruiz, S. A. Heterocycles 1999, 51, 2079-
2090. (b) Cadenas-Pliego, G.; Rosales-Hoz, M.-J.; Contreras, R.;
Flores-Parra, A. Tetrahedron Asymmmetry 1994, 5, 633-640. (c)
Cadenas-Pliego, G.; Mart´ınez-Aguilera, L. M. R.; Bello-Ram´ırez, A.
M.; Rosales-Hoz, M.-J.; Contreras, R.; Daran, J. C.; Halut, S.; Flores-
Parra, A. Phosphorus, Sulfur Silicon Relat. Elem. 1993, 81, 111-
123. (d) Cadenas-Pliego, G.; Contreras, R.; Flores-Parra, A.; Daran,
J. C.; Haut, S. Phosphorus, Sulfur Silicon Relat. Elem. 1993, 84, 9-15.
(3) (a) Flores-Parra, A.; Sanchez-Ruiz, S.; Guadarrama-Pe´rez, C. Eur. J.
Inorg. Chem. 1999, 2063-2069. (b) Flores-Parra, A.; Sanchez-Ruiz,
S.; Guadarrama-Pe´rez, C.; No¨th, H.; Contreras, R. Eur. J. Inorg. Chem.
1999, 2069-2073. (c) Guadarrama-Pe´rez, C.; Cadenas-Pliego, G.;
Mart´ınez-Aguilera, L. M. R.; Flores-Parra, A. Chem. Ber. 1997, 130,
813-817. (d) Mart´ınez-Aguilera, L. M. R.; Cadenas-Pliego, G.;
Contreras, R.; Flores-Parra, A. Tetrahedron Asymmetry 1995, 6, 1585-
1592. (e) Flores-Parra, A.; Cadenas-Pliego, G.; Mart´ınez-Aguilera, L.
M. R.; Garc´ıa-Nares, M. L.; Contreras, R. Chem. Ber. 1993, 126, 863-
867. (f) Flores-Parra, A.; Farfa´n, N.; Herna´ndez-Bautista, A. I.;
Ferna´ndez-Sa´nchez, L.; Contreras, R. Tetrahedron 1991, 47, 6903-
6914.
Many reports describe the reaction products of amino
alcohols and organoaluminum compounds, and a variety of
10.1021/ic034642+ CCC: $25.00 © 2003 American Chemical Society
Published on Web 10/21/2003
Inorganic Chemistry, Vol. 42, No. 23, 2003 7569

Ga´lvez-Ruiz et al.
Scheme 1
obtainned at -60 °C. Atomic form factors for neutral C, N, O and
H were taken from ref 7. Hydrogen atoms were found on difference
electron density maps. Crystallographic data (excluding struc-
ture factors) have been deposited with the Cambridge Crystal-
lographic Data Bank as nos. CCDC216396-CCDC216400. Copies
of the data can be obtained free of charge on application to 12
Union Road, Cambridge CB2 1EZ, U.K. [Fax: int. Code +
44(1223)336-033. E-mail: deposit@ccdc.cam.ac.uk.] Some crys-
tallographic data and bond lengths and angles are found in Tables
1 and 2.
Scheme 2
2-(1,3,5-Dithiazinan-5-yl)ethanol, 1. General Procedure. To
a solution of ethanolamine (10 mL, 0.17 mol) in water (50 mL) at
5 °C was slowly added a cool solution (5 °C) of NaSH (27.9 g,
0.50 mol) in aqueous formaldehyde (37%, 62.3 mL, 0.83 mol).
The reaction mixture was stirred for 30 min at 0 °C and 24 h at
room temperature. The white solids were removed by filtration,
washed with water, dissolved in CHCl3, and dried with sodium
sulfate. After the evaporation of solvent, compound 1 was obtained
as colorless crystals. Yield: 24.6 g, 95.2%. Mp 39 °C. Anal. Calcd
for C5H11NOS2: C, 36.36; H, 6.67; N, 8.48. Found: C, 36.24; H,
6.94; N, 8.44. 1H NMR (CDCl3) δ(ppm) ) 4.32 (s, 4H, 2H-4, 2H-
6), 3.99 (s, 2H-2), 3.54 (t, 3J ) 5.2 Hz, 2H-8), 3.08 (t, 2H-7, 3J )
5.2 Hz), 2.67 (s, H9). 13C NMR δ(ppm) ) 58.84 (C-8), 58.36 (C4,
C6), 51.30 (C7), 33.80 (C2). 15N NMR δ ) -352.91.
structures have been reported indicating a versatile and
complex reaction behavior.4 It is established that four main
structures a-d (Scheme 2) are possible, depending on the
stoichiometry, chelate size, basic character of the terminal
heteroelement, steric demand of the ligand, and aluminum
organic groups. Equilibria in solution between different
species make it difficult to establish their structures even
with the use of 27Al NMR. Herein, we are reporting new
polyfunctional ligands and their reactions with AlMe3 and
AlMe2Cl with the aim to add information about the behavior
of thiadiazinanes toward these organoaluminum compounds
and their coordination chemistry. We are also interested in
the study of interactions in the solid state of organic
molecules bearing weakly acidic protons atoms;5 therefore,
we will discuss relevant weak interactions of dithiazinane
C-H protons and donors atoms.
(()2-(1,3,5-Dithiazinan-5-yl)-1-methylethanol, 2. Compound
2 was prepared from 2-propanol amine (40 mL, 0.51 mol) following
the general procedure. Crystals were obtained from CHCl3. Yield:
69 g, 75%. Mp 70 °C. Anal. Calcd for C6H13S2NO: C, 40.19; H,
7.31; N, 7.82. Found: C, 40.07; H, 7.79; N, 7.83. 1H NMR
(CDCl3): δ ) 4.32 (s, 4H, 2H-4, 2H-6), 3.99 (s, 2H-2), 3.54 (qdd,
2
3
3J ) 6.2, 9.9, 2.9 Hz, H-8), 3.08 (dd, J ) 13.5, J ) 2.9 Hz,
2
3
H-7A), 2.67 (s, 1H-10), 2.4 (dd, J ) 13.5, J ) 9.9 Hz, H-7B),
1.15 (d, J ) 6.2 Hz, 3H-9). 13C NMR (CDCl3): δ ) 63.6 (C-8),
3
58.7 (s br, C-4, C-6), 57.2 (C-7), 33.7 (C-2), 20.1 (C-9). 15N NMR
(CHCl3): δ ) -310.6.
(()5-(1,3,5-Dithiazinan-5-yl)-1-phenylethanol, 3. Compound
3 was prepared from 2-phenyl-2-ethanolamine (10 g, 72.9 mmol).
Reaction afforded a syrup which crystallized from CHCl3. Yield:
12.3 g, 70%. Mp 56-58 °C. Anal. Calcd for C11H15NOS2: C, 54.74;
Experimental Section
Instrumentation. All solvents were freshly distilled before use.
The 1H, 13C, and 27Al NMR spectra were recorded with JEOL GXS-
270 (1H 270 MHz) or JEOL Eclipse (1H 400 MHz) and Bruker
1
H, 6.26; N, 5.80. Found: C, 54.44; H, 6.33; N, 5.92. H NMR
3
(CDCl3): δ ) 7.4-7.2 (s br, 5H), 4.60 (dd, J ) 13.5, 2.9 Hz,
(1H 300 MHz) instruments. H and 13C δ (ppm) are referenced to
1
2
H-8), 4.31 (s br, 2H-4, 2H-6), 4.00 (s br, 2H2), 3.49 (dd, J )
TMS, and Al(OH)63+ is the reference for 27Al. Melting points were
measured on a Gallenkamp apparatus and are uncorrected. Ele-
mental analyses were performed by Oneida Research Services,
Whitesboro, New York.
3
3
2
13.5, J ) 2.9 Hz, H-7A), 3.63 (s, H-9), 2.81 (dd, J ) J ) 13.5
Hz, H-7B). 13C NMR (CDCl3): δ ) 141.8 (Ci), 128.2 (2Cm), 127.2
(Cp), 125.6 (2Co), 69.5 (C-8), 58.8 (s br, C-4, C-6), 57.1 (C-7),
33.4 (C-2). 15N NMR (CDCl3): δ ) -333.5.
X-ray Crystallography. Crystal data were obtained with an
Enraf-Nonius Kappa CCD or a Siemens-P4 diffractometer both
equipped with area detectors. Computations for compounds 4, 10,
and 16-18 were performed by SHELXS-97 (Sheldrick 1990) and
SHELXL-97 programs (Sheldrick 1997).6 Structures of 4, 10, 16,
and 17 were obtained at room temperature, and that for 18 was
General Procedure for the Synthesis of Organoaluminum
Compounds 4-7. Using anhydrous conditions, N2 atmosphere, the
aluminum reagent AlMe2R (R ) Me or Cl) [2 M in hexane, 1 or
2 equiv] was slowly added with a hypodermic syringe to a stirred
solution of 2-(1,3,5-dithiazinan-5-yl)ethanol 1-3 (1 equiv) in
toluene at -40 °C. Stirring was continued for 30 min. The resulting
mixtures were filtered, and the solvent was evaporated to give
crystalline solids.
Preparation of Compounds 4-9: Bis[O-dimethylaluminum-
2-(1,3,5-dithiazinan-5-yl)-ethanolate], 4. To compound 1 (0.21
g, 1.24 mmol) in toluene (20 mL) was added a solution of AlMe3
(0.76 mL, 2 M in hexane, 1.24 mmol). On standing, crystals
(4) (a) Gelbrich, T.; Hecht, E.; Thiele, K.-H.; Sieler, J. J. Organomet.
Chem. 2000, 595, 21-30. (b) Francis, J. A.; Bott, S. G.; Barron, A.
R. J. Chem. Soc., Dalton Trans. 1998, 3305-3310. (c) Thiele, K.-H.;
Gelbrich, T.; Du¨michen, U. J. Organomet. Chem. 1997, 540, 89-94.
(d) Sierra, M. L.; Mel, V. S. J.; Oliver, J. P. Organometallics 1989,
8, 2486-2488. (e) McMahon, C. N.; Bott, S. G.; Barron, A. R. J. Chem.
Soc., Dalton Trans. 1998, 3301-3304. (f) Robson, D. A.; Bylikin, S.
Y.; Cantuel, M.; Male, N. A.; Rees, L. H.; Mountford, P.; Schro¨der,
M. J. Chem. Soc., Dalton Trans. 2001, 157-169.
(5) (a) Salas-Coronado, R.; Va´zquez-Badillo, A.; Medina-Garc´ıa, M.;
Garc´ıa-Colo´n, J. G.; No¨th, H.; Contreras, R.; Flores-Parra, A.
THEOCHEM 2001, 259-275. (b) Gu¨izado-Rodr´ıguez, M.; Flores-
Parra, A.; Tapia-Benavides, R.; Contreras, R.; Bakhmutov, V. I. Inorg.
Chem. 2001, 40, 3243-3246.
(6) Sheldrick, G. M. SHELXL-97 Program for Crystal Structure Refine-
ment; University of Go¨ttingen: Go¨ttingen, Germany, 1997; release
97-2.
(7) International Tables for X-ray Crystallography; Kynoch Press: Bir-
mingham, England, 1994; Vol. IV.
7570 Inorganic Chemistry, Vol. 42, No. 23, 2003

2-(1,3,5-Dithiazinan-5-yl)ethanol Al Complexes
Table 1. Crystal Data and Data Collection of Compounds 4, 10, and 16-18
4
10
16
17
18
formula
fw
C14H32Al2N2O2S4
196.72
0.3 × 0.2 × 0.2
colorless plate
monoclinic
P21/c
9.8132(12)
4.7213(17)
15.9375(18)
107.275(2)
2198.5(4)
4
C10H25Al25NOS2‚C7H8
192.76
0.4 × 0.3 × 0.2
colorless prism
monoclinic
P21
7.0182(9)
13.8168(17)
11.9208(12)
94.602(2)
1152.2(2)
4
C9H22Al2ClNOS2
313.81
0.4 × 0.23 × 0.12
colorless prism
monoclinic
C2/c
24.776(5)
8.115(2)
17.165(3)
107.94(3)
3283.4(12)
8
C10H24Al2ClNOS2
327.83
0.3 × 0.2 × 0.2
colorless prism
orthorhombic
P212121
10.727(2)
11.636(2)
14.411(3)
C15H26Al2ClNOS2
403.80
0.2 × 0.2 × 0.2
colorless prism
monoclinic
P21/c
cryst size (mm3)
cryst color
cryst syst
space group
a (Å)
9.767(2)
b (Å)
c (Å)
14.021(3)
15.429(3)
96.85(3)
2097.8(7)
4
1.279
0.468
857
â (deg)
V (Å3)
1798.8(6)
4
1.211
0.530
696
Z
F
calcd (Mg/m3)
1.337
0.522
944
1.111
0.311
416
1.270
0.577
1328
µ (mm-1
F(000)
)
scan type
T (K)
hemisphere
193(2)
hemisphere
193(2)
æ + ω scan
293(2)
æ + ω scan
293(2)
æ + ω scan
293(2)
2θ range, (deg)
3.84-58.06
-12 e h e 12
18 e k e 19
-18 e l e 19
12616
4407
2131
0.1121
4.52-58.14
-8 e h e 8
-17 e k e 17
-10 e l e 16
6709
3902
2132
0.0650
6.90-54.98
-31 e h e 26
-10 e k e 10
-21 e l e 22
27340
3759
2707
0.0594
7.00-54.94
-13 e h e 13
-15 e k e 15
-18 e l e 18
4088
4088
3284
0.0000
7.16-54.94
-12 e h e 11
-17 e k e 18
-20 e l e 18
15268
4752
3226
0.0453
index ranges
reflns collected
indep reflns
obsd reflns
R(int)
final R1 (4σ)
final wR2
GOF
R1 ) 0.1062
R2 ) 0.2409
1.045
R1 ) 0.0613
R2 ) 0.1234
0.966
R1 ) 0.0442
R2 ) 0.1286
0.929
R1 ) 0.0408
R2 ) 0.0869
1.032
R1 ) 0.0581
R2 ) 0.1484
1.017
3
2
separated from the solution which proved to be compound 4.
Yield: 0.26 g, 95%. Mp 208-210 °C. Anal. Calcd for C14H32-
Al2N2O2S4: C, 37.99; H, 7.29; N, 6.33. Found: C, 38.21; H, 7.39;
N, 6.09. 1H NMR (C6D6) δ(ppm) ) 4.08 (s br, 4H, 4H-2), 4.44 (s
br, 4H, 2H-4ax, 2H-6ax), 4.35 (s br, 4H, 2H-4eq, 2H-6eq), 3.74-
2.40 (m, 8H, 4H-7, 4H-8), -0.87 (s br, 12H, 4CH3). 13C NMR
δ(ppm) ) 56.7 (2C8), 56.2 (2C4, 2C6), 48.5 (2C7), 32.1 (2C2),
-1.1 (4CH3). 27Al NMR δ(ppm) ) 70 (∆1/2 ) 3240 Hz).
10H, Ph), 5.18 (dd, J ) 12.1, 4.2, 2H, H-8), 5.13 (d, J ) 14.8,
2
2
2H, H-6ax), 4.84 (d, J ) 13.9, 2H, H-4ax), 4.40 (dd, J ) 12.1,
3J ) 4.2, 2H, H-7A), 4.34 (d, 2J ) 13.7, 2H, H-2ax), 4.28 (d br, 2J
) 14.8, 2H, H-6eq), 3.84 (d br, 2J ) 13.9, 2H, H-4eq), 3.40 (d br,
2J ) 13.7, 2H, H-2eq), 2.75 (t, 2J ) 3J ) 12.1, 2H, H-7B), -1.08
(s br, CH3). 13C NMR δ(ppm) ) 138.9 (2Ci), 127.8 (4Co), 128.8
(4Cm), 128.4 (2Cp), 69.4 (2C8), 56.8 (2C4), 53.6 (2C6), 53.2 (2C7),
32.0 (2C2), -10.2 (s br, 2CH3). 27Al NMR δ(ppm) ) 59 (∆1/2
)
Bis[O-dimethylaluminum-1-phenyl-2-(1,3,5-dithiazinan-5-yl)-
ethanolate], 5, was prepared from compound 3 (0.33 g, 1.54 mmol)
and AlMe3 (0.77 mL, 2 M in hexane, 1.54 mmol). Compound 5
was obtained as a solid. Yield: 0.43 g, 95%. Mp 73-76 °C. Anal.
Calcd for C26H40Al2N2O2S4: C, 52.50; H, 6.78; N, 4.71. Found:
C, 52.25; H, 7.03; N, 4.92. 1H NMR (CDCl3) δ(ppm) ) 4.83 (dd,
9260 Hz).
General Procedure for Preparation of Compounds 8 and 9.
O-Dimethylaluminum-1-methyl-2-(1,3,5-dithiazinan-5-yl)eth-
anolate, 8. Compound 2 (0.45 g, 2.54 mmol) dissolved in toluene
(20 mL) and AlMe3 (1.27 mL, 2 M in hexane, 2.54 mmol) were
mixed. A white solid precipitated which was isolated by filtration
and recrystallized from toluene. Yield: 0.54 g, 90%. Mp 202-
204 °C. Anal. Calcd for C8H18AlNOS2: C, 40.83; H, 7.71; N, 5.95.
2
3J ) 11.4 and 4.0, 2H, H-8), 4.61 (d br, J ) 12.7, 4H, 2H-4ax,
2
2
2H-6ax), 4.40 (d br, J ) 12.8, 2H, H-2ax), 4.08 (dd, J ) 12.7
3
2
1
and J ) 4.0, 2H, H-7A), 3.92 (d br, J ) 12.7, 4H, 2H-4eq, 2H-
6eq), 3.50 (d br, 2J ) 12.8, 2H, H-2eq), 2.73 (dd, 2J ) 12.7 and 3J
) 11.4, 2H, H-7B), -1.05 (s br, 12H, 4CH3). 13C NMR δ(ppm) )
140.5 (2Ci), 127.7 (4Co), 129.1 (4Cm), 128.4 (2Cp), 70.2 (2C8),
58.3 (2C6), 54.6 (2C7), 54.0 (2C4) 32.7 (2C2), -9.56 (s br, 4CH3).
27Al NMR δ(ppm) ) 87 (∆1/2 ) 3780 Hz).
Found: C, 41.64; H, 7.81; N, 4.83. H NMR (CDCl3) δ(ppm) )
4.48 (s br, 5H, 2H-4, 2H-6, H-8), 4.00 (s br, 1H, H-7A), 3.61 (s
br, 2H, H-2), 2.45 (s br, 1H, H-7B), 1.36 (s, 3H, CH3), -0.83 (s
br, 6H, 2CH3). 13C NMR δ(ppm) ) 63.3 (C8), 58.6 (C4 and C6),
54.5 (C7), 32.8 (C2), 21.8 (CH3), -8.7 (s br, 2CH3). 27Al NMR
δ(ppm) ) 120 (∆1/2 ) 480 Hz).
Bis[O-methylchloroaluminum-2-(1,3,5-dithiazinan-5-yl)eth-
anolate], 6, was prepared from compound 1 (0.42 g, 2.54 mmol)
and AlMe2Cl (0.24 mL, 2.54 mmol). Compound 6 was obtained
as a solid. Yield: 0.55 g, 90%. Mp 170 °C (dec). Anal. Calcd for
C12H26Al2Cl2N2O2S4: C, 29.81; H, 5.42; N, 5.79. Found: C, 30.20;
H, 5.82; N, 5.59. 1H NMR (CDCl3) δ(ppm) ) 4.97-3.31 (m, 20H,
4H-2, 4H-4, 4H-6, 4H-7, 4H-8), -0.97 (s br, 4CH3). 27Al NMR
δ(ppm) ) 63 (∆1/2 ) 4550 Hz).
Bis[O-methylchloroaluminum-1-phenyl-2-(1,3,5)-dithiazinan-
5-yl-ethanolate], 7, was prepared from compound 3 (0.25 g, 1.02
mmol) and AlMe2Cl (0.1 mL, 1.02 mmol). Compound 7 was
obtained as a solid. Yield: 0.31 g, 95%. Mp 80-84 °C. Anal. Calcd
for C24H34Al2Cl2N2O2S4: C, 45.35; H, 5.39; N, 4.41. Found: C,
45.16; H, 5.13; N, 3.95. 1H NMR (CDCl3) δ(ppm) ) 7.4-7.3 (m,
O-Methylchloroaluminum-1-methyl-2-(1,3,5-dithiazinan-5-
yl)ethanolate, 9, was prepared from compound 2 (0.53 g, 2.95
mmol) and AlMe2Cl (0.27 mL, 2.95 mmol). Compound 9 was
obtained as a solid. Yield: 0.67 g, 89%. Mp 242 °C (dec). Anal.
Calcd for C7H15AlClNS2O: C, 32.87; H, 5.91; N, 5.48. Found: C,
32.60; H, 5.84; N, 5.00. 1H NMR (CDCl3) δ(ppm) ) 5.00 (d, 2J )
14.7, H-6ax), 4.85 (d, 2J ) 14.1, H-4ax), 4.36 (d, 2J ) 13.8, H-2ax),
2
3
2
4.24 (dd, J ) 11.5, J ) 4.0, H-7A), 4.18 (m, H-8), 3.86 (dd, J
4
2
4
) 14.7, J ) 2.1, H-6eq), 3.84 (dd, J ) 14.1, J ) 2.1, H-4eq),
2
4
2
3
3.44 (dt, J ) 13.8, J ) 2.1, H-2eq), 2.37 (t, J ) J ) 11.5,
H-7B), 1.21 (d, J ) 5.8, 3H, CH3), -0.73 (s br, 3H, CH3). 13C
3
NMR δ(ppm) ) 62.8 (C8), 56.9 (C4), 53.5 (C6), 53.1 (C7), 32.0
(C2), 21.0 (CH3), -8.8 (s br, 2CH3). 27Al NMR δ(ppm) ) 128
(∆1/2 ) 3520 Hz).
Inorganic Chemistry, Vol. 42, No. 23, 2003 7571

Ga´lvez-Ruiz et al.
Table 2. Values of Bond Lengths (Å) and Angles (deg) for Compounds 4, 10, and 16-18
4
S(1)-C(6)
1.806(9)
1.798(8)
1.798(9)
1.808(8)
1.818(6)
1.977(8)
2.936(3)
1.906(6)
1.975(9)
1.416(9)
1.48(1)
S(1)-C(2)
1.835(9)
1.80(1)
C(6)-S(1)-C(2)
98.2(4)
97.3(4)
76.6(2)
99.4(3)
102.7(3)
39.0(2)
114.2(3)
76.4(2)
99.6(3)
99.3(3)
39.5(2)
115.2(3)
126.6(5)
102.9(3)
128.1(4)
111.9(6)
112.9(6)
112.6(6)
111.8(4)
C(4)-S(3)-C(2)
98.6(4)
S(3)-C(4)
S(3)-C(2)
C(12)-S(11)-C(16)
O(19)-Al(1)-O(9)
O(9)-Al(1)-C(10)
O(9)-Al(1)-C(9)
O(19)-Al(1)-Al(2)
C(10)-Al(1)-Al(2)
O(9)-Al(2)-O(19)
O(19)-Al(2)-C(110)
O(19)-Al(2)-C(19)
O(9)-Al(2)-Al(1)
C(110)-Al(2)-Al(1)
C(8)-O(9)-Al(2)
Al(2)-O(9)-Al(1)
C(18)-O(19)-Al(2)
C(6)-N(5)-C(4)
C(12)-S(13)-C(14)
O(19)-Al(1)-C(10)
O(19)-Al(1)-C(9)
C(10)-Al(1)-C(9)
O(9)-Al(1)-Al(2)
C(9)-Al(1)-Al(2)
O(9)-Al(2)-C(110)
O(9)-Al(2)-C(19)
C(110)-Al(2)-C(19)
O(19)-Al(2)-Al(1)
C(19)-Al(2)-Al(1)
C(8)-O(9)-Al(1)
C(18)-O(19)-Al(1)
Al(1)-O(19)-Al(2)
C(6)-N(5)-C(7)
97.1(4)
120.9(3)
114.4(3)
123.7(3)
37.57(16)
114.8(2)
119.0(3)
116.7(4)
123.9(4)
36.91(17)
111.4(3)
129.8(5)
127.7(5)
104.1(3)
112.4(6)
114.9(6)
109.2(6)
109.3
S(11)-C(12)
S(13)-C(12)
Al(1)-O(19)
Al(1)-C(10)
Al(1)-Al(2)
Al(2)-O(19)
Al(2)-C(19)
O(19)-C(18)
N(5)-C(4)
S(11)-C(16)
S(13)-C(14)
Al(1)-O(9)
Al(1)-C(9)
Al(2)-O(9)
Al(2)-C(110)
O(9)-C(8)
N(5)-C(6)
N(5)-C(7)
N(15)-C(14)
C(2)-H(2A)
1.841(8)
1.815(8)
1.916(6)
2.000(8)
1.837(5)
1.958(8)
1.420(9)
1.43(1)
1.491(9)
1.48(1)
0.9900
N(15)-C(17)
N(15)-C(16)
1.44(1)
1.50(1)
C(4)-N(5)-C(7)
C(17)-N(15)-C(16)
S(3)-C(2)-S(1)
C(17)-N(15)-C(14)
C(14)-N(15)-C(16)
S(3)-C(2)-H(2A)
16
C(2)-S(3)
C(4)-N(5)
C(6)-N(5)
C(7)-N(5)
C(8)-O(9)
O(9)-Al(1)
Al(2)-Cl(1)
N(5)-Al(1)
1.794(4)
1.495(3)
1.494(3)
1.497(3)
1.446(3)
1.827(2)
2.178(1)
2.059(2)
O(9)-Al(2)
C(2)-S(1)
C(4)-S(3)
C(6)-S(1)
C(7)-C(8)
C(9)-Al(1)
C(10)-Al(1)
C(11)-Al(2)
C(12)-Al(2)
1.847(2)
1.803(4)
1.802(3)
1.806(3)
1.505(4)
1.938(3)
1.945(3)
1.960(3)
1.972(3)
S(3)-C(2)-S(1)
N(5)-C(4)-S(3)
C(6)-N(5)-C(4)
C(4)-N(5)-C(7)
C(4)-N(5)-Al(1)
C(8)-O(9)-Al(1)
Al(1)-O(9)-Al(2)
O(9)-Al(1)-C(10)
O(9)-Al(1)-N(5)
C(10)-Al(1)-N(5)
O(9)-Al(2)-C(12)
O(9)-Al(2)-Cl(1)
C(12)-Al(2)-Cl(1)
C(2)-S(3)-C(4)
113.1(2)
115.9(2)
109.6(2)
111.2(2)
111.6(2)
113.9(2)
125.7(1)
111.4(1)
87.43(8)
110.1(1)
105.8(1)
102.24(8)
109.6(1)
97.8(2)
N(5)-C(6)-S(1)
N(5)-C(7)-C(8)
O(9)-C(8)-C(7)
C(6)-N(5)-C(7)
C(6)-N(5)-Al(1)
C(7)-N(5)-Al(1)
C(8)-O(9)-Al(2)
O(9)-Al(1)-C(9)
C(9)-Al(1)-C(10)
C(9)-Al(1)-N(5)
O(9)-Al(2)-C(11)
C(11)-Al(2)-C(12)
C(11)-Al(2)-Cl(1)
C(2)-S(1)-C(6)
115.8(2)
109.2(2)
107.9(2)
113.1(2)
108.5(1)
102.7(2)
120.2(2)
110.6(1)
123.0(2)
108.4(1)
108.0(1)
119.6(2)
110.1(1)
98.2(2)
10
S(1)-C(2)
1.722(8)
1.803(6)
1.810(4)
1.952(6)
1.892(4)
1.975(6)
1.410(7)
1.464(7)
1.335(8)
1.36(1)
S(1)-C(6)
1.807(6)
1.804(9)
1.932(6)
2.079(4)
1.973(7)
1.984(6)
1.455(7)
1.474(6)
1.33(1)
C(2)-S(1)-C(6)
O(9)-Al(1)-C(10)
C(10)-Al(1)-C(9)
C(10)-Al(1)-N(5)
O(9)-Al(2)-C(13)
C(13)-Al(2)-C(11)
C(13)-Al(2)-C(12)
C(8)-O(9)-Al(1)
Al(1)-O(9)-Al(2)
C(7)-N(5)-C(4)
C(7)-N(5)-Al(1)
C(4)-N(5)-Al(1)
N(5)-C(4)-S(3)
C(8)-C(7)-N(5)
C(19)-C(14)-C(15)
C(15)-C(14)-C(20)
C(15)-C(16)-C(17)
C(17)-C(18)-C(19)
95.7(3)
112.5(2)
120.7(3)
108.0(2)
104.5(2)
113.1(3)
113.4(3)
114.5(4)
126.1(2)
110.9(5)
102.1(4)
109.5(3)
116.4(4)
119.1(6)
118.2(8)
121(1)
C(4)-S(3)-C(2)
96.8(3)
114.6(3)
86.6(2)
S(3)-C(4)
S(3)-C(2)
O(9)-Al(1)-C(9)
O(9)-Al(1)-N(5)
C(9)-Al(1)-N(5)
O(9)-Al(2)-C(11)
O(9)-Al(2)-C(12)
C(11)-Al(2)-C(12)
C(8)-O(9)-Al(2)
C(7)-N(5)-C(6)
C(6)-N(5)-C(4)
C(6)-N(5)-Al(1)
S(1)-C(2)-S(3)
Al(1)-O(9)
Al(1)-C(9)
Al(2)-O(9)
Al(2)-C(11)
O(9)-C(8)
N(5)-C(6)
C(7)-C(8)
C(14)-C(15)
C(15)-C(16)
C(17)-C(18)
Al(1)-C(10)
Al(1)-N(5)
Al(2)-C(13)
Al(2)-C(12)
N(5)-C(7)
108.7(2)
105.1(2)
101.5(2)
117.2(3)
119.2(4)
113.1(6)
109.8(5)
111.1(3)
113.3(4)
116.4(4)
115.0(6)
121(1)
N(5)-C(4)
C(14)-C(19)
C(14)-C(20)
C(16)-C(17)
C(18)-C(19)
1.51(1)
1.34(2)
1.35(1)
1.33(25)
1.35(2)
N(5)-C(6)-S(1)
C(7)-C(8)-O(9)
C(19)-C(14)-C(20)
C(16)-C(15)-C(14)
C(16)-C(17)-C(18)
C(14)-C(19)-C(18)
121.0(9)
120(1)
121.7(9)
120(1)
119(1)
17
Cl(1)-Al(2)
S(1)-C(2)
S(3)-C(2)
Al(1)-C(10)
Al(1)-N(5)
Al(2)-C(12)
O(9)-C(8)
N(5)-C(4)
2.201(1)
1.800(5)
1.810(5)
1.945(4)
2.030(2)
1.959(3)
1.469(3)
1.494(4)
S(1)-C(6)
S(3)-C(4)
Al(1)-O(9)
Al(1)-C(11)
Al(2)-O(9)
Al(2)-C(13)
N(5)-C(7)
N(5)-C(6)
1.799(3)
1.797(4)
1.845(2)
1.949(4)
1.855(2)
1.974(3)
1.486(4)
1.498(3)
C(6)-S(1)-C(2)
O(9)-Al(1)-C(10)
C(10)-Al(1)-C(11)
C(10)-Al(1)-N(5)
O(9)-Al(2)-C(12)
C(12)-Al(2)-C(13)
C(12)-Al(2)-Cl(1)
C(8)-O(9)-Al(1)
Al(1)-O(9)-Al(2)
C(7)-N(5)-C(6)
C(7)-N(5)-Al(1)
C(6)-N(5)-Al(1)
O(9)-C(8)-C(7)
O(9)-C(8)-C(9)
C(9)-C(8)-C(7)
97.6(2)
116.7(1)
120.3(2)
108.1(1)
114.8(1)
118.5(2)
106.3(1)
114.2(2)
121.2(1)
112.7(2)
99.7(2)
C(4)-S(3)-C(2)
O(9)-Al(1)-C(11)
O(9)-Al(1)-N(5)
C(11)-Al(1)-N(5)
O(9)-Al(2)-C(13)
O(9)-Al(2)-Cl(1)
C(13)-Al(2)-Cl(1)
C(8)-O(9)-Al(2)
C(7)-N(5)-C(4)
C(4)-N(5)-C(6)
C(4)-N(5)-Al(1)
S(1)-C(2)-S(3)
N(5)-C(4)-S(3)
N(5)-C(6)-S(1)
N(5)-C(7)-C(8)
98.5(1)
111.6(2)
85.52(9)
108.6(1)
102.7(1)
102.10(7)
111.3(1)
122.9(2)
112.4(2)
110.1(2)
111.9(2)
113.3(2)
115.5(2)
115.4(2)
110.3(2)
109.7(2)
108.2(2)
111.2(3)
109.8(3)
7572 Inorganic Chemistry, Vol. 42, No. 23, 2003

2-(1,3,5-Dithiazinan-5-yl)ethanol Al Complexes
Table 2 (Continued)
18
C(17)-Al(2)
C(17A)-Al(2)
C(2)-S(1)
2.045(8)
1.969(15)
1.802(4)
1.484(4)
1.493(4)
1.491(4)
1.458(3)
1.392(4)
1.954(4)
1.940(4)
1.946(3)
2.095(3)
C(2)-S(3)
1.801(4)
1.797(3)
1.807(3)
1.509(4)
1.509(4)
1.375(5)
1.394(5)
1.362(6)
1.355(6)
1.378(5)
1.852(2)
1.860(2)
2.188(2)
S(1)-C(2)-S(3)
N(5)-C(4)-S(3)
N(5)-C(6)-S(1)
N(5)-C(7)-C(8)
O(9)-C(8)-C(9)
C(9)-C(8)-C(7)
C(14)-C(9)-C(10)
C(10)-C(9)-C(8)
C(12)-C(11)-C(10)
C(12)-C(13)-C(14)
C(4)-N(5)-C(7)
C(7)-N(5)-C(6)
C(7)-N(5)-Al(1)
C(8)-O(9)-Al(1)
Al(1)-O(9)-Al(2)
O(9)-Al(1)-C(15)
O(9)-Al(1)-N(5)
C(15)-Al(1)-N(5)
O(9)-Al(2)-C(17A)
O(9)-Al(2)-C(17)
C(17A)-Al(2)-C(17)
112.2(2)
117.0(2)
116.2(2)
110.1(2)
111.9(2)
111.7(3)
118.8(3)
121.7(3)
120.0(3)
120.6(4)
112.8(2)
112.4(2)
101.9(2)
116.6(2)
120.2(1)
109.6(2)
85.2(1)
O(9)-C(8)-C(7)
107.6(2)
119.5(3)
119.7(3)
120.3(4)
97.5(2)
C(4)-S(3)
C(14)-C(9)-C(8)
C(9)-C(10)-C(11)
C(13)-C(12)-C(11)
C(4)-S(3)-C(2)
C(6)-S(1)
C(4)-N(5)
C(6)-N(5)
C(7)-N(5)
C(8)-O(9)
C(9)-C(10)
C(15)-Al(1)
C(16)-Al(1)
C(18)-Al(2)
N(5)-Al(1)
C(7)-C(8)
C(8)-C(9)
C(9)-C(14)
C(10)-C(11)
C(11)-C(12)
C(12)-C(13)
C(13)-C(14)
O(9)-Al(1)
O(9)-Al(2)
Al(2)-Cl(1)
C(2)-S(1)-C(6)
C(9)-C(14)-C(13)
C(4)-N(5)-C(6)
97.2(2)
120.5(4)
109.8(2)
108.5(2)
111.0(2)
121.5(2)
119.2(2)
124.0(2)
103.9(2)
116.7(1)
125.1(4)
117.3(3)
93.62(8)
100.8(3)
107.9(1)
114.5(1)
C(4)-N(5)-Al(1)
C(6)-N(5)-Al(1)
C(8)-O(9)-Al(2)
O(9)-Al(1)-C(16)
C(16)-Al(1)-C(15)
C(16)-Al(1)-N(5)
O(9)-Al(2)-C(18)
C(18)-Al(2)-C(17A)
C(18)-Al(2)-C(17)
O(9)-Al(2)-Cl(1)
C(17A)-Al(2)-Cl(1)
C(18)-Al(2)-Cl(1)
C(17)-Al(2)-Cl(1)
106.0(2)
106.8(4)
104.6(3)
13.7(3)
General Procedure for Compounds 10-15. O-Dimethyl-
aluminum-O-trimethyl-aluminum-2-(1,3,5-dithiazinan-5-yl)-
ethanolate, 10. Compound 1 (0.36 g, 2.2 mmol) dissolved in
toluene (20 mL) and AlMe3 (2.2 mL, 2 M in hexane, 4.4 mmol)
were mixed. A white solid was obtained which was recrystallized
from toluene at room temperature. Yield: 0.59 g, 92%. Mp 184-
186 °C. Anal. Calcd for C10H25Al2NOS2: C, 40.94; H, 8.59; N,
4.77. Found: C, 40.88; H, 8.18; N, 4.80. 1H NMR (CDCl3) δ(ppm)
) 3.80 (d, 2J ) 13.6, 2H, H-4ax, H-6ax), 3.51 (d, 2J ) 13.6, H-2ax),
3.39 (t, 3J ) 5.6, 2H, H-8), 3.13 (d br, 2J ) 13.6, 2H, H-4eq, H-6eq),
2.80 (t, J ) 5.6, 2H, H-7), 2.50 (d br, J ) 13.6, H-2eq), -0.58
(s br, 5CH3). 13C NMR δ(ppm) ) 58.1 (C8), 55.1 (C4, C6), 48.5
(C7), 30.2 (C2), - 8.4 (br, 5CH3). 27Al NMR δ(ppm) ) 156 (∆1/2
) 4860 Hz).
O-Dimethylchloroaluminum-O-methylchloroaluminum-2-(1,3,5-
dithiazinan-5-yl)-ethanolate, 13, was prepared from compound 1
(0.28 g, 1.70 mmol) and AlMe2Cl (0.32 mL, 3.40 mmol).
Compound 13 was crystallized from toluene. Yield: 0.51 g, 90%.
Mp 141-144 °C. Anal. Calcd for C8H19Al2Cl2NOS2: C, 28.75;
1
H, 5.73; N, 4.19. Found: C, 28.76; H, 5.68; N, 3.96. H NMR
(CDCl3) δ(ppm) ) 4.64 (d, 2J ) 13.9, 2H, H-4ax, H-6ax), 4.40 (d,
2J ) 14.0, H-2ax), 4.10 (t, 3J ) 5.6, 2H, H-8), 4.05 (dd, 2J ) 13.9,
3J ) 2.3, 2H, H-4eq, H-6eq), 3.77 (t, 3J ) 5.6, 2H, H-7), 3.55 (dt,
2J ) 14.0, 3J ) 2.3, H-2eq), -0.53 (s, 3CH3). 13C NMR δ(ppm) )
59.5 (C8), 55.8 (C4, C6), 47.9 (C7), 31.4 (C2), -10.0 (s br, 3CH3).
27Al NMR δ(ppm) ) 129 (∆1/2 ) 3440 Hz).
3
2
O-Dimethylchloroaluminum-O-methylchloroaluminum-1-meth-
yl-2-(1,3,5-dithiazinan -5-yl)-ethanolate, 14, was prepared from
compound 2 (0.36 g, 2.00 mmol) and AlMe2Cl (0.76 mL, 4.00
mmol). Compound 14 was crystallized from toluene. Yield: 0.73
g, 95%. Mp 103-106 °C. Anal. Calcd for C9H21Al2Cl2NOS2: C,
O-Dimethylaluminum-O-trimethylaluminum-1-methyl-2-(1,3,5-
dithiazinan-5-yl)- ethanolate, 11, was prepared from compound
2 (0.33 g, 1.82 mmol) and AlMe3 (1.82 mL, 2 M in hexane, 3.64
mmol). Compound 11 was crystallized from toluene. Yield: 0.47
g, 85%. Mp 179-181 °C. Anal. Calcd for C11H27Al2NOS2: C,
1
31.04; H, 6.08; N, 4.02. Found: C, 31.05; H, 6.12; N, 3.82. H
NMR (CDCl3) δ(ppm) ) 4.62 (d, 2J ) 13.9, H-6ax), 4.54 (d, 2J )
1
42.98; H, 8.85; N, 4.56. Found: C, 42.68; H, 8.65; N, 4.61. H
2
3
2
14.0, H-4ax), 4.37 (dd, J ) 12.0, J ) 4.0, H-7A), 4.35 (d, J )
NMR (CDCl3) δ(ppm) ) 4.56 (d, 2J ) 14.1, H-6ax), 4.49 (d, 2J )
3
2
13.9, H-2ax), 4.34 (ddq, J ) 12.0, 6.5 and 4.0, H-8), 4.07 (dt, J
14.6, H-4ax), 4.31 (d, 2J ) 14.6, H-2ax), 4.30 (dd, 2J ) 11.6, 3J )
) 14.0, 4J ) 2.0, 2H, H-4eq), 3.96 (dt, 2J ) 13.9, 4J ) 2.0, H-6eq),
2
5.9, H-7A), 4.21 (m, H-8), 3.99 (d br, J ) 14.1, H-6eq), 3.97 (d
2
4
2
3
3.48 (dt, J ) 13.9, J ) 2.0, H-2eq), 2.69 (t, J ) J ) 12.0,
H-7B), 1.47 (d, 3J ) 6.5, 3H, CH3), -0.67 (s br, 3CH3). 13C NMR
δ(ppm) ) 67.2 (C8), 57.7 (C4), 54.7 (C6), 54.2 (C7), 31.4 (C2),
21.2 (CH3), -7.9 (s br, CH3), -7.0 (s br, CH3). 27Al NMR δ(ppm)
) 129 (∆1/2 ) 2500 Hz).
2
2
2
br, J ) 14.6, H-4eq), 3.49 (d br, J ) 14.6, H-2eq), 2.67 (dd, J
3
3
) 11.6, J ) 5.9, H-7B), 1.42 (d, J ) 5.9, CH3), -0.84 (s br,
5CH3). 13C NMR δ(ppm) ) 66.8 (C8), 57.8 (C7), 54.8 (C6), 54.7
(C4), 31.5 (C2), 21.4 (CH3), -7.6 (br, 5CH3). 27Al NMR δ(ppm)
) 171 (∆1/2 ) 7740 Hz).
O-Dimethylchloroaluminum-O-methylchloroaluminum-1-phen-
yl-2-(1,3,5-dithiazinan-5-yl)-ethanolate, 15, was prepared from
compound 3 (0.43 g, 1.80 mmol) and AlMe2Cl (0.68 mL, 7.20
mmol). Compound 15 was crystallized from toluene. Yield: 0.63
g, 85%. Mp 96-99 °C. Anal. Calcd for C14H23Al2Cl2NOS2: C,
O-Dimethylaluminum-O-trimethylaluminum-1-phenyl-2-(1,3,5-
dithiazinan-5-yl)-ethanolate, 12, was prepared from compound 3
(0.43 g, 1.80 mmol) and AlMe3 (3.6 mL, 2 M in hexane, 7.20
mmol). Compound 12 was crystallized from toluene. Yield: 0.60
g, 90%. Mp 140-144 °C. Anal. Calcd for C16H29Al2NOS2‚1/
2C7H8: C, 52.01; H, 7.91; N, 3.79. Found: C, 52.40; H, 8.33; N,
3.90. 1H NMR (CDCl3) δ(ppm) ) 7.4-7.3 (m, 5H, Ph), 5.17 (dd,
3J ) 8.9, 5.0, H-8), 4.57 (d, 2J ) 14.3, H-6ax), 4.51 (d, 2J ) 14.3,
H-4ax), 4.30 (d, 2J ) 13.4, H-2ax), 4.26 (dd, 2J ) 13.6, 3J ) 5.0,
H-7A), 4.17 (d br, 2J ) 14.3, H-6eq), 3.83 (d br, 2J ) 14.3, H-4eq),
3.47 (d br, 2J ) 13.4, H-2eq), 3.40 (dd, 2J ) 13.6, 3J ) 8.9, H-7B),
-1.11 (s, CH3), -0.85 (s, CH3). 13C NMR δ(ppm) ) 139.0 (Ci),
126.4 (Cm), 128.8 (Cp), 128.7 (Co), 72.6 (C8), 57.1 (C4), 55.6 (C6),
54.9 (C7), 31.5 (C2), -7.9 (s br, CH3), -7.1 (s br, CH3). 27Al NMR
δ(ppm) ) 150 (∆1/2 ) 2350 Hz).
1
40.98; H, 5.65; N, 3.41. Found: C, 40.44; H, 6.00; N, 3.36. H
NMR (CDCl3) δ(ppm) ) 7.4-7.2 (m, 5H, Ph), 5.27 (dd, 3J ) 15.0,
2
2
4.0, H-8), 4.68 (d, J ) 13.9, H-4ax), 4.67 (d, J ) 14.3, H-6ax),
2
3
2
4.58 (dd, J ) 14.3, J ) 4.0, H-7A), 4.39 (d, J ) 13.9, H-2ax),
4.31 (dd, 2J ) 14.3, 3J ) 15.0, H-7B), 4.10 (d br, 2J ) 13.9, H-4eq),
3.19 (d br, 2J ) 13.9, H-2eq), 3.18 (d br, 2J ) 14.3, H-6eq), -0.39
(s, CH3), -0.30 (s, CH3). 13C NMR δ(ppm) ) 136.3 (Ci), 129.4
(Cm), 128.4 (Cp), 127.4 (Co), 73.8 (C8), 57.2 (C4), 53.9 (C6), 54.7
(C7), 31.5 (C2), -9.6 (s br, CH3), -7.6 (s br, CH3). 27Al NMR
δ(ppm) ) 130 (∆1/2 ) 9370 Hz).
Inorganic Chemistry, Vol. 42, No. 23, 2003 7573

Ga´lvez-Ruiz et al.
General Procedure for Preparation of Compounds 16-18.
O-Dimethylchloro-aluminum-O-dimethyl aluminum-2-(1,3,5-
dithiazinan-5-yl)ethanolate, 16. Compound 16 was obtained two
ways: (a) The first way is from compound 1 (0.51 g, 3.07 mmol)
in toluene (20 mL) and AlMe3 (1.54 mL, solution 2 M in hexane,
3.07 mmol) at -78 °C. After stirring for 15 min, AlMe2Cl (0.29
mL, 3.07 mmol) was added. The suspension was stirred for another
15 min and filtered and the solvent evaporated. (b) Alternatively,
compound 1 (0.51 g, 3.07 mmol) dissolved in toluene (20 mL)
and AlMe2Cl (0.29 mL, 3.07 mmol) added by syringe were mixed
at -78 °C and stirred for 15 min. Then, AlMe3 (1.54 mL, solution
2 M in hexane, 3.07 mmol) was added. After stirring for another
15 min, the suspention was filtered and the solvent evaporated from
the filtrate. Compound 16 was obtained as a white solid. Yield:
0.87 g, 90%. Mp 250 °C (dec). Anal. Calcd for C9H22Al2ClNOS2:
C, 34.45; H, 7.07; N, 4.46. Found: C, 34.68; H, 6.95; N, 4.31. 1H
Figure 1. ORTEP representation of compound 4 with coordinated bond
lengths of 2.470 Å (N5fAl2) and 2.476 Å (N15fAl1).
Scheme 3
2
NMR (CDCl3) δ(ppm) ) 4.62 (d, J ) 13.8, 2H, H-4ax, H-6ax),
4.38 (d, 2J ) 14.0, H-2ax), 4.10 (m, 2H, H-8), 4.00 (dd, 2J ) 13.8,
2
3
3J ) 2.2, 2H, H-4eq, H-6eq), 3.51 (dt, J ) 14.0, J ) 2.2, 2H,
H-2eq), 3.70 (m, 2H, H-7), -0.69 (s, 4CH3). 13C NMR δ(ppm) )
58.8 (C8), 55.6 (C4, C6), 48.2 (C7), 31.3 (C2), -9.3 (s br, 4CH3).
27Al NMR δ(ppm) ) 160 (∆1/2 ) 7810 Hz).
O-Dimethylchloroaluminum-O-dimethylaluminum-1-methyl-
2-(1,3,5-dithiazinan-5-yl)ethanolate, 17, was prepared from com-
pound 2 (0.34 g, 1.92 mmol), AlMe3 (0.96 mL, 2 M in hexane,
1.92 mmol), and AlMe2Cl (0.18 mL, 1.92 mmol), by the two
procedures described for compound 16. Compound 17 crystallized
from CHCl3. Yield: 0.60 g, 95%. Mp 103-106 °C. Anal. Calcd
for C10H24Al2ClNOS2: C, 36.64; H, 7.38; N, 4.27. Found: C, 36.43;
H, 7.41; N, 4.61. 1H NMR (CDCl3) δ(ppm) ) 4.64 (d, 2J ) 13.9,
for a pentacoordinated aluminum atom at 70 ppm (∆1/2 3240
Hz). From the toluene solution, crystals were separated that
have been characterized by X-ray diffraction as dimeric
pentacoordinated aluminum compound 4, Figure 1 and
Scheme 3.
The molecular structure of 4 shows that the aluminum
atoms reside in the center of a distorted trigonal bipyramidal,
tbp, arrangement with one oxygen and one nitrogen atom in
apical positions [O9-Al1-N15, 152.6(3)°; C9-Al1-O19,
116.7(4)°; C9-Al1-C10, 123.7(3)°; C10-Al1-O19,
120.9(3)°]. The oxygen atoms are bridging the aluminum
atoms forming a four-membered ring. The apical Al-O
bonds are longer (O9-Al1, 1.916(6) Å; Al2-O19, 1.906(6)
Å) than the equatorial bonds (O9-Al2, 1.837(5) Å; Al1-
O19, 1.818(6) Å). The dithiazinane rings have a chair
conformation with the aluminum atoms in equatorial position.
The distances N-Al [N5-Al2, 2.470 Å and N15-Al1, 2.476
Å] are exceptionally long with respect to other reported
values (2.1-2.3 Å).4 An explanation can be found in the
partial tetrahedral character (70%) of the nitrogen atom that
corresponds to a weak base due to the more p character of
the nitrogen orbital involved in the coordinative bond, and
to the steric effect produced by the dithiazinane cycle.
Evidence for a coordinative bond is also based in the
direction of the nitrogen lone pair toward the aluminum
nuclei and the geometry around the aluminum atoms. The
alanoxazolidine rings have an envelope conformation, with
C7 and C17 outside the plane. Intermolecular CH‚‚‚S
hydrogen bonds [2.979 Å] were observed, Figure 2. These
C-H‚‚‚S interactions are similar to CH‚‚‚O interactions
which are now accepted as relevant in crystal engineering.9
2
2
H-4ax), 4.57 (d, J ) 14.4, H-6ax), 4.37 (d, J ) 14.0, H-2ax),
4.34 (m, H-8), 4.41 (dd, 2J ) 11.2, 3J ) 4.5, H-7A), 4.12 (dt, 2J )
14.4, 4J ) 2.0, H-6eq), 4.00 (dt, 2J ) 13.9, 4J ) 2.0, H-4eq), 3.52
2
4
2
3
(dt, J ) 14.0, J ) 2.0, H-2eq), 2.71 (dd, J ) 11.2, J ) 10.9,
3
H-7B), 1.51 (d, J ) 5.9, CH3), -0.66 (s br, 2CH3), -0.60 (s br,
2CH3). 13C NMR δ(ppm) ) 67.1 (C8), 57.6 (C4), 54.5 (C6), 54.1
(C7), 31.4 (C2), 21.1 (CH3), -8.3 (s br, 2CH3), -7.0 (s br, 2CH3).
27Al NMR δ(ppm) ) 163 (∆1/2 ) 8330 Hz).
O-Dimethylchloroaluminum-O-dimethylaluminum-1-phenyl-
2-(1,3,5-dithiazinan-5-yl)ethanolate, 18, was prepared from com-
pound 3 (0.35 g, 1.40 mmol), AlMe3 (0.72 mL, 2 M in hexane,
1.40 mmol), and AlMe2Cl (0.13 mL, 1.40 mmol). Compound 18
crystallized from toluene. Yield: 0.46 g, 85%. Mp 106-108 °C.
Anal. Calcd for C15H26NS2OAl2Cl: C, 46.21; H, 6.72; N, 3.59.
1
Found: C, 45.92; H, 7.01; N, 3.41. H NMR (CDCl3) δ(ppm) )
7.5-7.1 (m, 5H, Ph), 5.24 (dd, 3J ) 10.0, 4.6, H-8), 4.66 (d, 2J )
2
3
13.9, 2H, H-4ax, H-6ax), 4.50 (dd, J ) 13.5, J ) 4.6, H-7A),
2
2
4.34 (d br, J ) 13.9, H-4eq), 3.98 (d, J ) 14.0, H-2ax), 3.95 (d
br, J ) 13.9, H-6eq), 3.49 (d br, J ) 14.0, H-2eq), 3.21 (dd, J
2
2
2
3
) 13.5, J ) 10.0, H-7B), -1.0 (s br, 2CH3), -0.4 (s br, 2CH3).
13C NMR δ(ppm) ) 137.3 (Ci), 126.2 (Cm), 128.9 (Cp), 128.6 (Co),
73.0 (C8), 57.2 (C4), 54.7 (C6), 54.3 (C7), 31.5 (C2), -9.9 (s br,
2CH3), -7.5 (s br, 2CH3). 27Al NMR δ(ppm) ) 152 (∆1/2 ) 6260
Hz).
Results and Discussion
Equimolar Reactions. AlMe3 or AlMe2Cl was reacted
with compounds 1-3, in toluene at -40 °C. Examination
by 27Al NMR of the equimolar reaction of compound 1 with
AlMe3 gave two signals, one at 9.0 ppm (∆1/2 ≈ 300 Hz)
which corresponds to an hexacoordinated and symmetrical
aluminum atom bonded to oxygen atoms,8 and a broad signal
(8) (a) Akitt, J. W. In Annual Reports on NMR Spectroscopy; Mooney E.
F., Ed.; Academic Press Inc.: London, 1972; Vol. 5A, p 465. (b)
Atwood, D. A.; Jegier, J. A.; Liu, S.; Rutherford, D.; Wei, P.; Tucker,
R. C. Organometallics 1999, 18, 976. (c) Krossing, I. Ph.D. Thesis,
Fakulta¨t fu¨r Chemie und Pharmazie, Ludwig-Maximilians-Universita¨t,
Mu¨nchen, Germany, 1997. (d) Kumar, R.; de Mel, V. S. J.; Sierra,
M. L.; Hendershot, D. G.; Oliver, J. P. Organometallics 1994, 13
2079-2083.
7574 Inorganic Chemistry, Vol. 42, No. 23, 2003

2-(1,3,5-Dithiazinan-5-yl)ethanol Al Complexes
pyridine.4b,e,10b 1H and 13C NMR spectra of compounds 8
and 9 indicate only one isomer in each case; therefore, this
can be attributed to a stereroselective synthesis or to a
dynamic equilibrium toward the more stable isomer. The
dithiazinane ring in compound 8 is in conformational
equilibrium, whereas 9 is in a anchored conformation with
diasterotopic groups C4 and C6. This is attributed to a weaker
NfAlMe2 bond with respect to NfAlMeCl. We did not
find evidence of dimeric structures of type b at room
temperature, see a following discussion (Scheme 2). The
different behavior of compounds 8 and 9 toward dimerization
could be attributed to an electronic effect. For compounds 8
and 9, methyl (electron releasing) substituted ligand 2 may
bind to an aluminum atom with more electronic donation
from oxygen to aluminun resulting in a metal atom less
electronic deficient that keeps the compounds as monomers.
Reactions with 2 equiv of the Aluminum Compounds.
The combination of ligands 1 or 2 with 2 equiv of the
aluminum reagents afforded the dimetalated derivatives 10-
11 and 13-14 while ligand 3 was only completely trans-
formed into derivatives 12 and 15 using 4 equiv of aluminum
reagents (Scheme 5). The reaction products have one
aluminum atom chelated by the aminoalkoxide unit and a
second aluminum atom coordinated to the oxygen of the ring.
The structure of compounds 10-15 was determined by
NMR. They show only one broad signal in the 27Al spectra
indicating a fluxional behavior of the aluminum atoms. In
Figure 2. S‚‚‚H hydrogen bonds (2.97 Å) in the lattice of compound 4.
Scheme 4
The combination of 1-3 and AlMe2Cl and AlMe3 yields
the dimeric pentacoordinated aluminum derivatives 4-7 as
white powders, Scheme 4. The pentacoordination of the
aluminum atom is deduced from the characteristic 27Al
1
resonances (59-87 ppm).4b,e,10 The H NMR spectra show
the absence of the signal for the O-H protons; the H-7 and
H-8 atoms show complex coupling patterns of an anchored
conformation attributed to the bonding of oxygen and
nitrogen atoms to the aluminum centers. Compounds 5 and
7 present the anchored dithiazinane in a chair conformation
as is deduced from the different signals for equatorial and
axial hydrogen atoms and their coupling patterns. An
interesting fact in 5 and 7 is that hydrogen atoms H-7A are
deshielded with respect to H-7B (about 1.3-1.6 ppm), and
this may be due to their position pointing to sulfur atoms,
as found in the solid state structure of compound 4, Figure
8. The 13C NMR spectra of 5 and 7 (R ) Ph) show only
one isomer indicating a stereoselective reaction; diasterotopic
signals for C4 and C6 of the dithiazinane rings (5, δ ) 58.3
ppm and 54.0; 7, δ ) 53.6 and 56.8 ppm) are due to the
strong N-Al bond and the presence of the stereogenic atom
C8, and in 7 to the different substitution at aluminum
compound, Scheme 3.
1
the H spectrum of compounds 10-15, the chair preferred
conformation of the six-membered ring indicates a strong
NfAl bond which inhibits the nitrogen inversion.3 Com-
pounds 11, 12, 14, and 15 present diasterotopic C4 and C6
atoms due to the coordinative bond and the substitution at
C8.
The X-ray diffraction analysis of compound 10, crystal-
lized from toluene, reveals that the N-coordinated Al atom
resides in an equatorial position of the dithiazinane ring,
while the AlMe3 unit is bonded to a planar oxygen atom
(Figure 3a). The two Al-C bonds of the chelate are eclipsed
with N-C4 and N-C6 bonds; the methyl groups of the exo-
cyclic aluminum atom are present in a staggered conforma-
tion. The five-membered ring shows an envelope conforma-
tion with C8 out of the plane. In the unit cell, one molecule
of toluene is present in the asymmetric unit (Figure 3).
An intermolecular arrangement determined by π interac-
tions of protons at C2 and toluene is depicted in Figure 3b.
The contact distances in an edge-type interaction are similar
to those previously reported, then to three 3 C atoms.
Distances to CH2eq are 2.79, 2.74, and 2.80 Å.9,11
We have found that some mixed compounds can be
prepared by adding AlMe2Cl to 4-5 or by adding 1 equiv
of AlMe3 to compound 9. Reaction of compound 9 with
AlMe3 did not give the expected dialuminum derivative 19
but only compound 17 (Scheme 6). The result indicates that
the aluminum atoms have exchanged their sites or that a
chlorine atom has exchanged its position with a methyl
group.4
Equimolar reactions of compound 2 (in toluene at -40
°C) with AlMe3 and AlMe2Cl gave compounds 8 and 9
(Scheme 4). They are stable monomers (structure c, Scheme
2), as was established by comparison of their 27Al NMR data
(δ ) 120 for 8 and 128 for 9) with those of some
tetracoordinated aluminum compounds derived from hydroxy-
(9) (a) Desiraju, G. R. Acc. Chem. Res. 1996, 29, 441-449 and references
therein. (b) The Crystal as a Supramolecular Entity; Desiraju G. R.,
Ed.; John Wiley & Sons: Chichester, England, 1996; Vol. 2. (c)
Supramolecular Chemistry; Steed J. W., Atwood J. L., Eds.; John
Wiley & Sons: Chichester, England, 2000. (d) Viswamitra, M. A.;
Radhakrishnan, R.; Bandekar, J.; Desiraju, G. R. J. Am. Chem. Soc.
1993, 115, 4868-4869.
(10) Borrmann, H.; Persson, I.; Sandstro¨m, M.; Satålhandske, C. M. V. J.
Chem. Soc., Perkin Trans. 2 2000, 393-402.
(11) Koch, U.; Popelier, P. L. A. J. Phys. Chem. 1995, 99, 9747-9754.
Inorganic Chemistry, Vol. 42, No. 23, 2003 7575

Ga´lvez-Ruiz et al.
Figure 3. (a) View of compound 10 with a molecule of toluene with the N5fAl1 bond distance of 2.080 Å. (b) Polymeric array of molecules of 10
produced by π interactions of toluene with SCH2S protons. (The distances from H2eq are the following: to Cortho, 2.79 Å; to Cmeta, 2.74 Å; to Cpara 2.80
Å. The distance from H2ax to Cipso is 2.75 Å.).
Scheme 5
Scheme 6
Some variable temperature NMR experiments were per-
formed for compounds 17 and 18. By heating (100 °C in
toluene), the 27Al NMR spectra showed that the signals
become sharp, but their chemical shifts did not change. By
cooling in the same solvent, compound 17 at -70 °C did
not show, as expected, two different signals for each
aluminum atom, but they were completely transformed into
the pentacoordinated compound 20 (δ ) 54 ppm, ∆1/2 6400
Hz); the initial aspect of the spectrum was recovered by
coming back into room temperature (Scheme 6). The same
behavior was observed for compound 18 which was com-
pletely transformed at -50 °C into compound 5 (δ ) 59
ppm, ∆1/2 7600 Hz).
Compounds 16-18 crystallized from CDCl3 at room
temperature, and their structures were determined by X-ray
methods (Figures 4-9). In these three compounds, the
heterocyclohexane has a chair conformation with the alu-
minum atom in equatorial position, and the five-membered
ring has an envelope conformation. In compounds 16 and
7576 Inorganic Chemistry, Vol. 42, No. 23, 2003

2-(1,3,5-Dithiazinan-5-yl)ethanol Al Complexes
Figure 4. Crystal structure of compound 16: (a) ORTEP representation and (b) dimeric structure produced by S‚‚‚H8ax intermolecular interactions and
NfAl bond distances.
Figure 5. Crystal structure of compound 17: (a) ORTEP representation and (b) view of the conformation of the five-membered ring.
18, the atom C7 is out of the plane whereas in 17 the N
atom deviates from the ring plane. The N-Al bond lengths
are short indicating a strong coordinative bond particularly
for 16 and 17 (2.059 Å in 16, 2.030 Å in 17, and 2.095 Å
in 18); the longest bond length Al-O is the exocyclic bond
[in 16, Al1-O9 1.827(2) Å and Al2-O9 1.847(2) Å; in 17,
1.845(2) and 1.855(2) Å; and in 18, 1.852(2) and 1.860(2)
Å]. In compound 16, a dimeric arrangement was produced
by two S‚‚‚H8ax intermolecular hydrogen bonds, 2.99 Å
(Figure 4b). The latter is a significant C-H‚‚‚S hydrogen
bond if it is compared with data reported in the literature
(3.78 Å) for a similar hydrogen bond.9
In compound 17, the methyl substituent of the five-
membered ring is in a pseudoequatorial position (Figure 5).
The Al2-Cl bond is directed to a trans arrangement with
the C-Me bond [Cl1-Al2-C8-C-9, 147.75°]. The chlorine
atom Cl1 has an intramolecular hydrogen bond Cl1‚‚‚H10a,
2.945 Å (Figure 5b).
There are intermolecular cooperative network interactions
between three molecules through methylene protons and
chlorine atoms [Cl1‚‚‚H2b′, 2.936 Å and Cl1‚‚‚H4a′, 2.817
Å] and one Al-CH3 proton with sulfur [S3‚‚‚H10c,′ 2.999
Å] (Figure 6).
Figure 6. Intramolecular hydrogen bonds Cl‚‚‚H and S‚‚‚H10 between
three molecules of compound 17.
A dimeric array is produced by a π interaction centroid
type11 of the phenyl group of one molecule with the H2eq
of another molecule [2.760, 2.792, 2.843, and 2.896 Å]
(Figure 9). An intermolecular hydrogen bond was found
between Cl1‚‚‚H2ax, 2.77 Å. In the literature, C-H chlorine
intermolecular interactions have been proposed for distances
of 3.61 Å.9
The solid state structure of compound 18 is shown in
Figure 7. It shows short intramolecular contacts of proton
H7A and the sulfur atoms of the dithiazinane ring at 2.83
and 2.95 Å (Figure 8).
Conclusions
We have reported three new ligands bearing as a coordi-
nating motif a dithiazinane and an ethanol group. They were
Inorganic Chemistry, Vol. 42, No. 23, 2003 7577

Ga´lvez-Ruiz et al.
Figure 7. Crystal structure of compound 18: (a) ORTEP representation and (b) view showing the “heterocyclopentane” conformation.
Figure 9. Array of two molecules showing π interactions of compound
18.
Figure 8. Solid state structure of compound 18 showing the intramolecular
contact of proton H7A and the sulfur atoms of dithiazinanyl ring.
stereogenic center at the ethanolate group helped to evaluate
the N-Al coordination strength making evident the dia-
stereotopism at the methylene carbon atoms C4 and C6. The
27Al NMR spectra indicate the equilibrium between the two
alkyl aluminum groups for dinuclear compounds and the
preference of the Al-Cl bond in an exocyclic position.
Variable temperature experiments indicated a monomer-
dimer equilibrium.
effective coordinating agents for organoaluminum com-
pounds, and the resulting molecules showed different struc-
tures depending on the reagent ratio and the substitution at
the ethanol arm. Nitrogen and oxygen atoms are involved
in the coordination to Al atoms. We have obtained two
monomers and four dimers of aminoethanolate aluminum
compounds and nine dinuclear derivatives. We have observed
neither coordination to sulfur atoms nor opening of the
dithiazinanyl ring. We were unable to obtain the bis-
aminoethanolate structures d or the open structures a
(Scheme 2). X-ray diffraction studies were helpful in order
to establish the actual structures in the solid state and to give
evidence of intermolecular interactions C-H‚‚‚‚S, C-H‚‚‚‚Cl,
and C-H‚‚‚‚π found in the crystalline network. NMR
experiments have shown fluxional behavior for compounds
4, 6, and 8 and in others a static conformation of the
dithiazinane rings 5, 7, and 9-18. The presence of a
Acknowledgment. We thank Cinvestav and Conacyt-
Me´xico for financial support and scholarships for
J.C.G.-R. as well as Guillermo Uribe for recording some of
the spectra.
Supporting Information Available: Crystallographic data in
CIF format. This material is available free of charge via the Internet
at http://pubs.acs.org.
IC034642+
7578 Inorganic Chemistry, Vol. 42, No. 23, 2003