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MoII and Mo0 Complexes of 3 3 7 7 11 11 15 15-Octamethyl-1 5 9 13-tetrathiacyclohexadecane.

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yellow. Yellow-orange crystals suitable for X-ray investigation were obtained
by slow diffusion using ether as cosolvent.
Received: May 14, 1987;
supplemented: July 31, 1987 [Z 2238 IE]
German version: Angew. Chem. 99 (1987) 1208
LA. R
LB, R
=
Me
=
H
CAS Registry numbers:
2, 110827-87-1: 3, 110827-58-2;4, 110827-60-6;5, 110827-62-8;6, I10827-639: Rh2ClL(CO),, 14523-22-9; COD, 1 1 1-78-4; PPhs, 603-35-0: H2, 1333-74-0;
cyclooctane, 292-64-8: I-hexene, 592-41-6.
[ I ] R. R. Burch, E. L. Muetterties, J. Am. Chem. Soc. 104 (1982) 4257.
121 S . 1. Hommeltoft, D. H. Berry, R. Eisenberg, J. Am. Chem. SOC.108
(1986) 8345.
[3] R. R. Schrock, J. A. Osborn, J. Am. Chem. SOC.93 (1971) 3089.
[4] N. E Dixon, W. C. Jackson, M. J. Lancaster, G. A. Lawrence, A. M.
Sargeson, Inory. Chem. 20 (1981) 471.
[S) J. Nitzschke, S. P. Schmidt, W. C. Trogler, Inory. Chem. 24 (1985) 1972.
[6] C. P. Casey, R. M. Bullock, F. Nief, J. Am. Chem. Soc. 105 (1983) 7574.
[7] Crystal data: triclinic, a = 14.218(4), b = 16.012(4), c = 13.543(4) A,
u =96.80(2), p = 109.16(2), y=84.38(2)', V=2893 A', Z = 2 , pcnjcd= 1.527.
1 2 6 3 6 r e f l e c t i o n s ( + h ~ k l , 3 ° < B < 2 7 0 ) m e a s u r e dat -100°C; 7302 with
I > 3o(I) used for structure determination and refinement. Experimental
absorption corrections. H atoms in computed cooordinates
B(H)= I Beqv(c) A2. No hydrogen atom parameter was
(C-H =0.95
allowed to vary during refinement. Anisotropic temperature factors for
all non-hydrogen atoms. R(F)=0.068, Rb,(F)=0.08I, with o(F2)=
[d,,",,, +(008 p)21,
GOF= 1.34.
A,
+
[trans-Mo(CO),L,] 3
+
Mo" and Moo Complexes of
3,3,7,7,11,11,15,15-0ctarnethyl-l,5,9,13tetrathiacyclohexadecane**
By Toshikatsu Yoshida,* Tomohiro Adachi, Tatsuo Ueda,
Megumi Watanabe, Manabu Kaminaka. and
Taiichi Higuchi*
Recently, macrocyclic polythioethers as a ligand in transition-metal complexes have received considerable interest
in view of the enormously high redox petentials found for
the Cu'"'I and Co"12.31complexes and the ability to stabilize the metals in low oxidation states such as Rh'.'4,51 The
high nucleophilicity of the square-planar Rh' cationic
complexes of 1,4,8,1I-tetrathiacyclotetradecane and its
6,6,13,13-tetramethyl analogue as proved by a facile oxidative addition of CH2C12 is also remarkable since
[RhCI(PPh&] and [Rh(tBuNC),]'
are inert toward
CH2CI, .Is1 These salient features may promise a rich chemistry of macrocyclic polythioether complexes of transition
metals, particularly in low oxidation states. In view of
current interest in Mo complexes of sulfur ligands, we
have prepared the novel monomeric Moll dihalo complexes 1 and 2 of 3,3,7,7,11,11,15,15-octamethyl-1,5,9,13[frans-MoX,L,] 1 , X = B r ; 2, X=CI
tetrathiacyclohexadecane, LA. The Mo" halo complexes
of thioethers so far reported, e.g., [ M o ~ C I ~ ( S E and
~~)~]
[Mo6CI 2(dithiahexane)2]are polymeric.161
[*] Prof. Dr. T. Yoshida, T. Adachi, T. Ueda, M. Watanabe, M. Kaminaka
[**I
Cyclic voltammetry shows that both 1 and 2 exhibit extraordinarily high redox potentials for the Mo"'/Mo" (ca.
1.2 V vs. SCE) and Mo"/Mo' (ca. -0.2 v) couples,
which emphasizes the possibility that 1 and 2 might serve
as potential precursors for syntheses of lower-valent molybdenum complexes containing the thioether as ligand. In
fact, both chemical and electrochemical reductions of 1
under C O atmosphere afforded 3 . Complex 3 represents
Department of Chemistry, Faculty of Integrated Arts and Sciences
University of Osaka Prefecture
Sakai, Osaka 591 (Japan)
Prof. Dr. T. Higuchi
Department o f Chemistry, Faculty of Science, Osaka City University
Sumiyoshi, Osaka 588 (Japan)
This work was supported by a Grant-in-Aid (60470048 and 61125005)
for Scientific Research from the Ministry of Education, Japan. T. A . and
T. H.are indebted to the Crystallographic Research Center, Institute of
Protein Research and Computation Center, Osaka University, for computer calculations.
Angew. Chem l n t . Ed. Engl. 26 (1987)
No. 11
the first example of a Mo" dicarbonyl complex of a
thioether
ligand,
since
all
known
complexes
[Mo(CO),(SR,),-.]
contain more than three C O ligands."]
The dimeric complex I M o ~ ( S H ) ~ ( L ~ ) ~ ] ' ' is
[ * ~the only
known Mo" complex of a 16-membered cyclic tetrathioether. However, this complex cannot be a candidate
for the starting material mentioned above.
The Mo" dibromo complex l l 9 l was prepared by treating
[MoBr2(C0)& with two molar equivalents of
in toluene under reflux as paramagnetic, orange crystals (50%
yield based o n the ligand). Since the physical properties of
1,1'21
including magnetic, electronic spectral, and electrochemical data are similar to those of the dichloride 2 , a
trans geometry was proposed for 1 . A similar reaction of
[MoCI,(CO)~], with LA did not produce 2 ; instead, 4 was
obtained as paramagnetic, orange crystals (25% yield).LY,
The formation of 4 is rather expected since the reaction of
I~Qc-MoCI~L,]
4
[MoCI,(CO),] with a ligand of poor n-acceptor ability has
been known to proceed via disproportionation of Mo" to
Mo"' and Moo affording CO-free Mo"' c o m ~ l e x e s .Al~'~~
ternatively, 4 was obtained in a higher yield (71%) by treating [MoCI,(MeCN),] with LA in CH2C12at room temperature. Reduction of 4 with Zn powder in CH2C12took place
readily at room temperature to give 2 as paramagnetic,
yellow crystals (51% yield).",'21 The observation of a single
Mo-CI stretching band (V=306 cm-') in the IR spectrum
of 2 is consistent with a trans geometry.
The cyclic voltammogram of 1 and 2 measured in
MeCN (0.1 M nBu4NBF4) at a scan rate of IOOrnVs-'
shows two essentially reversible redox couples due to
Mo"/M'
-0.15 V vs. SCE, A E = 100 mV,
f,,,,,=0.92
for 1 and E l / , = -0.28 V, AE=75 mV,
Zpa/pc=1.08 for 2) and Mo"'/Mo"
1.21 V vs.
SCE, A E = 120 mV, I,,,,,= 1.00 for 1 and
1.19 V,
AE = 80 mV, I,,,,, = 1.22 for 2). The high redox potentials
compared with those of [trans-MoX2(Ph2PCH2CH2PPh,),j
[Mo"/Mo', E l / z = -1.51 V vs. SCE for X = B r and
- 1.68 V for X = C I ; Mo"'/Mo" , El,2 = +0.01 V for X = B r
and - 0.05 V for X = C1]"41 are remarkable and probably
due to the weak o-donating property of thioethers.I6] In addition, the ring size of the thioether may be responsible for
the high potentials as found for a series of the related Cu"
complexes.'"
0 VCH Verlaysgesellschaft mbH, 0-6940 Weinheim. 1987
+
0570-0833/87/1111-1171 $ 02.50/0
+
I171
Reduction of 1 with Na/Hg in T H F under C O atmosphere ( 1 atm CO) occurred at ambient temperature to give
3 as diamagnetic, red crystals quantitatively. Controlledpotential electrolysis of 1 at - 2.2 V vs. SCE in MeCN under C O also afforded 3 . Despite the similar redox potentials of 1 and 2 , reduction of 2 under similar conditions
employed for 1 gave only traces of 3 . The 'H- and I3Cindicate a planar coordination of LA
NMR spectra of 3['21
with "all up" conformation, the four 6-membered
I\;loSCH2CMe2CH2Srings assuming the chair form. This is
confirmed by an X-ray structural study of 3 (Figure
n
x
Cf26)
o(2)
Fig. I. Molecular structure of 3. Selected bond distances [A] and angles ["I:
Mo-S(I) 2.434(2), MO-S(5) 2.439(2), MO-S(9) 2.432(2), Mo-S(I3) 2.438(2);
S(9)-Mo-S( 13) 90. I ( I),
S(I)-Mo-S(S) 90.5(1), S(5)-Mo-S(9) 89. I( I),
S(I)-Mo-S(13) 90.0(1), S(I)-MoS(9) l75.l(l), S(5)-Mo-S(13) 175.5(1),
C(25)-Mo-C(26) 174.3(3), Mo-C(25)-0( I ) 174.3(7), Mo-C(26)-0(2) 173.0(7).
The geometry around the Mo atom is slightly distorted octahedral with two CO ligands in the axial positions, and
the molecule possesses approximately C,, symmetry. The
Mo atom is displaced toward the ring C atoms from the
least-squares plane defined by the four S atoms by
0.093(2) A. The plane defined by the four S atoms is
strictly planar, the deviatiop of the S atoms from the plane
being less than 0.002(2) A. The two Mo-C (Mo-C(26)
1.979(8) and Mo-C(25) 2.002(8) A) and C - 0 distances
(C(26)-0(2) 1.161(10) and C(25)-0(1) 1.144(10) A of two
mutually trans CO ligands are not sig?ificantly different.
The Mo-S distances (average 2.436(2) A) are considerably
shorter than those found in the Moo complexes
Vac-Mo(CO),( 1,4,7-trithiacyclononane)] (mean 2.520(6)
A)['] and [trans-Mo(N2),(PhzPCH2CH2SMe)(PMePh2),1
(2.483(3) A).1161Furthermore, the short Mo-S distances in
3 compared with the corresponding lengths in
(Mo~(SH)~(L,)~J'@
(mean 2.493(2) A)[*]are consistent with
the stronger d,-d, interaction in the Moo-S bond than in
the Mo"-S bond. It is to be noted that the trans geometry
of 3 is stable at room temperature, while [transMO(CO)~(P~,PCH,CH,PP~,),~
is known to isomerize readily into the cis i ~ o m e r . ~ ~ ' '
Received. May 19, 1987;
revised: August 31, 1987 [ Z 2250 IE]
German version: Angew. Chem. 99 (1987) 1182
CAS Registry numbers:
1, 110935-32-5; 2, 110935-33-6; 3, 110935-34-7; 4, 110935-35-8; LA, 11093537-0:
[MoBr,(CO)&,
80594-72-5:
[MoCI,(CO)&,
12655- 17-3 :
[MoCI,(MeCN):], 19187-82-7; disodium salt of 2,2-dimethyl-1,3-propanedithiolate, 1 10935-36-9; 1,3-dibromo-2,2-dimethyIpropane,
5434-27-5.
[ I ] T. E. Johnes, D. R. Rorabacher, L. A. Ochrymowycz, J . Am. Chem. Soc.
98 (1976) 4322.
[Z] J. R. Hartman, E. J. Hintsa, S. R. Cooper, J . Am. Chem. Soc. 108 (1986)
1208.
1172
0 VCH Verlagsgeselkhaff mbH. 0-6940 Wemheim. 1987
13) H.-J. Kiippers, A. Neves, C. Pomp, D. Ventur, K. Wieghardt, B. Nuber,
J. Weiss, Inorg. Chem. 25 (1986) 2400.
141 W. D. Lemke, K. E. Travis, N. E. Takvoryan, D. H. Busch, Adu. Chem.
Ser. 150 (1976) 358.
[5] T. Yoshida, T. Ueda, T. Adachi, K. Yamamoto, T. Higuchi, J . Chem.
Soc. Chem Commun. 1985. 1137.
[6] S . G . Murray, F. R. Hartley, Chem. Rev. 81 (1981) 365.
[7] M. T. Ashby, D. L. Lichtenberger, Inorg. Chem. 24 (1985) 636, and references cited therein.
[8] J. Cragel, V. B. Pett, M. D. Glick, R. E. DeSimmone, Inorg. Chem. 17
(1978) 2885.
191 Satisfactory elemental analyses for all new compounds were obtained.
[lo] LA was prepared by treating disodium 2,2-dimethyl-l.3-propanedithiolate and 1,3-dibromo-2,2-dimethylpropane
in EtOH by a similar procedure to that employed for the preparation of 1.5,9,13-tetrathiacyclohexadecane [ I I]. Purification of the concentrated reaction mixture by chromatography (silica gel, n-hexane as eluent) gave colorless crystals (16%
yield), m.p.= 165-166°C. 'H-NMR (60 MHz, CDCI,); 6 = 1.01(s, Me),
2.63(s, CHZ).
[ I I] L. A. Ochrymowycz, C.-P. Mak, J. D. Michna, J . Org. Chem. 39 (1974)
2079.
1121 1: m.p.=261-262"C (dec.); petl(CHCI3)=3.1 pB; UV/VIS (CHCI,):
A,,,(&)=320(5900), 495 nm (45); MS: m / z 666(Me), 586(MG- Br),
506(Mo-2Br). 2 : m.p.=212 "C(dec); p,lt(CHC13)=3.1 p e ; UV/VIS
(CHCI,): A,.,,(&)=334(4200), 457 nm (33); IR(CsBr): 5,,,.,,=306
cm-';
MS: m / z 576(Ma), 541(Me-CI), 506(Me-2CI). 3 : m.p.= 160"C(dec.);
'H-NMR (270 MHz, [D&oluene); 6=0.71 (s, 12 H ; Me), 1.12 ( s , 12 H ;
Me), 2.1 I (d, J = 11.0 Hz, 8 H; CH2), 2.46 (d, J= 11.0 Hz, 8 H ; CH,):
"C-NMR (67.8 MHz, [D&oluene): 6=23.0 (Me), 35.2 (Me), 38.5
(CH2),53.5(CMe2),ZZ2(CO);IR(THF): Vco= 1902(m), 1767(vs)cm-'.
4:
m.p.= 155"C(dec); petdCHCl3)=3.9p8;
UV/VIS (CHCI,):
A,,&)=290(2800),
453(160), 750 nm (25); IR(CsBr): 5,.,.,=290,
305
cm-'.
1131 D. Westland, N. Muriithi, Inorg. Chem. I 1 (1972) 2971.
[I41 T. I. Al-Salih, C. J. Pickett, J . Chem. Soc. Dalton Trans. 1985. 1255.
[IS] Crystal data for 3; orthorhombic, space group P 2 , 2 , 2 , , a = 14.380(5),
b = 10.876(5), c = 17.123(5) A, V=2678.0(17)
1.391 g cm-' for
2 = 4 ; p(MoK,)=7.93 c m - ' ; Rigaku AFC-6 with MoKn radiation
(A=O 71069
2687 independent reflections (2<28<50"), no absorption correction; Patterson method (UNICS), block-diagonal leastsquares refinement with anisotropic temperature factors for nonhydrogen atoms (263 parameters) with Fixed positional and thermal ( B = 4.0
parameters for hydrogen atoms, 2049 reflections
used (1>30(1)), R=0.035, R,=0.045,
Goodness of Fit=0.554;
@(max/min)=0.42/-0.30 e/A'. Further details of the crystal structure
investigation may be obtained from the Fachinformationszentrum Energie, Physik, Mathematik GmbH, D-7514 Eggenstein-Leopoldshafen2
(FGR), on quoting the depository number CSD-52750, the names of the
authors, and full citation of the journal.
[I61 R. H. Morris, J. M. Ressner, J. F. Sawyer, M. Shiralian, J. Am. Chem.
Soc. 106 (1984) 3683.
[I71 M. Sato, T. Tatsumi, T. Kodama, M. Hidai, T. Uchida, Y. Uchida, J .
Am. Chem Soc. I00 (1978) 4447.
A',
A);
A?)
IAs3Br12J3-and
Structurally Novel, Discrete Halogenoarsenate(~r~)
Ions
By William S . Sheldrick* and Hans-Joachim Hausler
The trihalides EX3 of the elements E=P, As, Sb, Bi are
capable of adding further halide ions X- to give a variety
of halogeno anions [EX,, 4"- (in mononuclear anions
with n = l , 2, 3, in polynuclear anions with n=1/4, 1/2,
2/3, 3/2 inter aha). In the case of the intensively studied
halogenoantimonate(1tr) complexes,['I both discrete anionst2' such as [Sb2CI9l3- or [Sb4C1,6]4- as well as polymeric anions, for example [Sb,F;],
or [Sb,I&[31 are
known. Characteristic of the stereochemistry of the individual Sb atoms is an octahedral coordination with three
shorter and three considerably longer trans-sited (secondary) Sb-X bonds.
[*] Prof. Dr. W. S . Sheldrlck, DipLChem. H.-J. Hausler
Fachbereich Chemie der Universitat
Erwin-Schrodinger-Strasse,
D-6750 Kaiserslautern (FRG)
0570-0833/87/1111-1172 $ 02.50/0
Angew. Chem. Int. Ed. Engl. 26 (1987) No. I 1
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