Facile metalation of silicon and germanium analogues of thiocarboxylic acids with a manganese(II) hydride precursor

Article abstract of DOI:10.1002/chem.201201335

Synthesis and characterization of the first manganese(II)-containing heavier thiocarboxylate analogues, [L^DipSi(=S)OMnL^Dep] (4; L^Dip=CH[C(Me)N(2,6-iPr₂C₆H₃)] ₂, L^Dep=CH[C(Me)N(2,6-Et₂C₆H ₃)]₂) and [L^DipGe(=S)OMnL^Dep] (5) are described. They are accessible through reaction of the silicon and germanium analogues of the respective thiocarboxylic acids [L^DipE(=S)OH] (E=Si, Ge) with the β-diketiminato (nacnac) manganese(II) hydride precursor [(L^DepMn)₂(μ-H)₂] (3) in high yield. The first Mn nacnac hydride 3 has been prepared by the reaction of manganese bromide [(L^DepMn)₂(μ-Br)₂] (2) with KBEt ₃H. Compounds 4 and 5 represent the first transition-metal heavier thiocarboxylates with the Si=S and Ge=S functionalities. All new compounds are paramagnetic and were characterized by elemental analysis, IR spectroscopy, MS (EI), and single-crystal X-ray diffraction analyses. Due to the N→E (E=Si, Ge) and E=S→Mn donor-acceptor interaction as well as the carboxylate-like π-electron delocalization within the E(S)O moieties, the E=S double bonds in these compounds are resonance stabilized. Active guys: The first transition-metal sila- and germathiocarboxylates were obtained by facile metalation of the corresponding heavier thiocarboxylic acids with currently unknown β-diketiminato manganese hydride. Preliminary investigations revealed that these complexes are capable of activating dioxygen and oxygenating triphenylphosphane at ambient temperature (see scheme). Copyright

Full text of DOI:10.1002/chem.201201335

FULL PAPER
DOI: 10.1002/chem.201201335
Facile Metalation of Silicon and Germanium Analogues of Thiocarboxylic
Acids with Manganese(II) Hydride Precursor
Shenglai Yao, Yun Xiong, and Matthias Driess*[a]
Abstract: Synthesis and characteriza-
tion of the first manganese(II)-contain-
ing heavier thiocarboxylate analogues,
ganese(II) hydride
precursor
thiocarboxylates with the Si=S and
Ge=S functionalities. All new com-
pounds are paramagnetic and were
characterized by elemental analysis, IR
spectroscopy, MS (EI), and single-crys-
tal X-ray diffraction analyses. Due to
the N!E (E=Si, Ge) and E=S!Mn
donor–acceptor interaction as well as
the carboxylate-like p-electron delocal-
ization within the E(S)O moieties, the
E=S double bonds in these compounds
are resonance stabilized.
[(LDepMn)
2A
The first Mn nacnac hydride 3 has
[LDipSi(=S)OMnLDep
]
(4;
LDip
LDep
=
been prepared by the reaction of man-
CH[C(Me)N(2,6-iPr2C6H3)]2,
=
ganese bromide [(LDepMn)
2ACTHNGUTERN(UNG m-Br)2] (2)
CH[C(Me)N(2,6-Et2C6H3)]2)
and
with KBEt3H. Compounds 4 and 5 rep-
resent the first transition-metal heavier
[LDipGe(=S)OMnLDep
]
(5) are de-
scribed. They are accessible through re-
action of the silicon and germanium
analogues of the respective thiocarbox-
ylic acids [LDipE(=S)OH] (E=Si, Ge)
with the b-diketiminato (nacnac) man-
Keywords: dioxygen activation
germanium · manganese · silicon ·
transition metals
·
Introduction
Due to the central importance of the carbonyl group in
chemistry, E=X double-bonds-containing species involving
heavier Group XIV elements E and Group XVI elements X
as heavier congeners of ubiquitous ketones, carboxylic acids,
and related species have attracted considerable interest.[1]
As a result, a vast number of striking examples containing
an E=X moiety (E=Si, Ge, Sn; X=O, S, Se, Te) has been
realized by taking advantage of thermodynamic stabilization
through donor–acceptor interaction and/or kinetic stabiliza-
tion by using sterically demanding substituents.[1] In this con-
text, starting from zwitterionic N-heterocyclic silylene[2] and
germylene,[3] we succeeded in synthesizing a series of com-
pounds containing doubly bonded silicon and germanium
with Group XVI elements including the isolation of the first
Si=O and Ge=O double-bond-containing complexes.[4]
Scheme 1. Silathiocarboxylic acid–DMAP adduct A and germathiocar-
boxylic acid B with a b-diketiminato ligand.
with elemental sulfur.[5b] Both carboxylic acid congeners A
and B contain a thermodynamically well-stabilized E=S unit
as illustrated by the respective resonance structure A’ and
B’ (Scheme 1). They are promising starting material for the
synthesis of new types of metal complexes, that is, metal si-
lathiocarboxylates. Their coordination ability toward metal
ions is expected to be different from those reported for re-
spective thiocarboxylates due to the presence of the E=S
subunits (E=Si, Ge). Metal complexes of A and B are
rare,[4i] and no transition-metal derivative has been reported
so far.
Through the reaction of
a
4-dimethylaminopyridine
(DMAP)-stabilized Si=O compound with hydrogen sulfide,
the isolable silathiocarboxylic acid A (Scheme 1) with a b-
diketiminato
ligand
LDip
(LDip =CH[C(Me)N(2,6-
iPr2C6H3)]2) was synthesized as DMAP adduct.[4i] The ger-
manium analogue B,[5a] which crystallized as a dimer through
two S···H hydrogen bonds has also been described by
Roesky and co-workers through the reaction of LDipGeOH
Of the vast number of classical metal carboxylates with
redox-active transition metals, manganese(II) species play
an interesting role as catalysts in chemical synthesis and are
of enormous importance in nature (e.g., water oxidation in
the photosystem II).[6] The versatile role of manganese com-
plexes in chemical and biological catalysis encouraged us to
[a] Dr. S. Yao, Dr. Y. Xiong, Prof. Dr. M. Driess
Institute of Chemistr, Metalorganics and Inorganic Materials
Sekr. C2, Technische Universitꢀt Berlin
Strasse des 17. Juni 135, 10623 Berlin (Germany)
Fax: (+49)30-314-29732
E-mail: matthias.driess@tu-berlin.de
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synthesize the first manganese derivatives of A and B. To
enable a straightforward metalation of A and B by poten-
tially suitable manganese(II) reagents in nonaqueous solu-
tions, various b-diketiminato (“nacnac”) Mn precursor com-
plexes have been tested. Recently, LMnX complexes (L=
nacnac, X=I,[7a,b] Cl, CH3COO, Me, Ph, C5H5,[7c]
lower than the theoretical value of 5.5 mB for a high-spin
MnII (S=5/2), implying the presence of an interaction be-
tween the two Mn centers in the dimeric molecule of 2.
Most likely, the dimers exist with the monomer [LDipMnBr]
in equilibrium in the benzene solution, as was supported by
cryoscopic measurement. In the MS (EI) spectrum,
[LDepMnBr]+ was observed at m/z=497 (86%), followed by
[LDepMn]+ (at m/z=416, 100%). The elemental analyses are
also consistent with the calculated values. The molecular
structure of 2 has been established by single-crystal X-ray
diffraction analysis. Complex 2 crystallized in the monoclinic
space group P21/n and showed a dimeric structure of
NACHTUNGTRENNUNG
(SiMe3)2,[7d] [(m-O)2MnL][8]) have been reported by the re-
search groups of Roesky and Power.[7a–d,8] We anticipated
that manganese hydrides would be best suited for clean met-
alation of A and B. Herein, we report the synthesis of the
first nacnac manganese hydride [LDepMnH] (3; LDep
=
CH[C(Me)N(2,6-Et2C6H3)]2) from the corresponding bro-
mide [(LDepMn)
CHTUNGTRENNUNG
a facile and clean metalation reagent to form the first heavi-
er thiocarboxylate analogues [LDipSi(S)OMnLDep] (4) and
[LDipGe(S)OMnLDep] (5).
Results and Discussion
Synthesis of b-diketiminato manganese bromide 2 and hy-
dride 3: The manganese bromide 2 is readily accessible
through a one-pot procedure by lithiation of 1 with nBuLi
followed by transmetalation with manganese dibromide in
diethyl ether (Scheme 2). After changing the solvent of the
Figure 1. Molecular structure of complex 2. Thermal ellipsoids are drawn
at 50% probability level. Hydrogen atoms are omitted for clarity. Select-
ꢀ
ꢀ
ed bond lengths [ꢂ] and angles [8]: Mn1 Br1 2.5543(4), Mn1’ Br1
ꢀ
ꢀ
ꢀ
2.5462(4), Mn1 N2 2.047(2), Mn1 N1 2.055(2), Mn1 Br1’ 2.5462(4),
ꢀ
ꢀ
ꢀ
ꢀ
N1 C2 1.328(3), N2 C4 1.330(3), C2 C3 1.410(3), C3 C4 1.397(3);
Mn1’-Br1-Mn1 86.00(1), N2-Mn1-N1 93.96(7), Br1’-Mn1-Br1 94.01(1),
C2-N1-Mn1 123.3(1), C4-N2-Mn1 122.5(2), N1-C2-C3 123.6(2), C4-C3-C2
130.7(2), N2-C4-C3 124.9(2). Symmetry transformations were used to
generate equivalent atoms with (’): ꢀx+1, ꢀy, ꢀz.
Scheme 2. Synthesis of b-diketiminato manganese bromide 2 and hydride
3.
[LDepMnBr] with two bromide bridges (Figure 1). Both man-
ganese centers adopt tetrahedral coordination geometry
with the slightly puckered six-membered C3N2Mn rings per-
pendicular to the four-membered Mn2Br2 ring. The Mn···Mn
distance is 3.478 ꢂ and is very close to that observed in bis-
resulting mixture to n-hexane, complex 2 can be easily iso-
lated as yellow crystals in 86% yield. It is worth to note that
the similar complex [(LDipMn)
G
(tetraphenylphosphonium) bisACHTGNUTERNNU(G m2-bromo)dibromo manga-
nese(II) (ca. 3.542 ꢂ).[10] The Mn Br bond lengths of
2.5462(4) and 2.5543(4) ꢂ in 2 are close to the correspond-
ing values observed in the latter complex (ca. 2.58 ꢂ). The
ꢀ
G
ACHTUNGTRENNUNG
ꢀ
Mn N bond lengths (2.047(2) and 2.0552(2) ꢂ) are also con-
C
sistent with those found in [(LDipMn)
(m-Cl)2] (2.0830(9) and
with the b-diketiminato potassium precursor.
2.0819(10) ꢂ)[7c] and [(LDipMn)
2ACHTUNGTRENNUNG
Complex 2 showed a paramagnetic 1H NMR spectrum
with very broad signals. The solution magnetic susceptibility
was found to be 3.6 mB per manganese center (Evans
method by using C6D6 as solvent).[9] The latter value is
ACHTUNGTRENNUNG
THF) in toluene at room temperature for 3 h led to the for-
mation of compound 3, which can be easily isolated as
yellow crystals in 77% yield. Similar to 2, compound 3 re-
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Metalation of Silicon and Germanium Analogues of Thiocarboxylic Acids
FULL PAPER
vealed also a paramagnetic 1H NMR spectrum with very
broad resonances. The solution magnetic-susceptibility mea-
surement showed 2.5 mB per manganese center, which is
much lower than the theoretical value of 5.5 mB for a high-
spin MnII. The difference between the observed and theoret-
ical meff values of 3 suggests an even stronger interaction be-
tween the two manganese centers than in 2. Similar
Mn···Mn interaction in a dimeric manganese hydride com-
plex has been suggested by Chomitz and Arnold.[11] The
Scheme 3. Synthesis of manganese silathiocarboxylate 4 and germathio-
carboxylate 5.
composition of
3
is confirmed by MS (EI) with
[(LDepMnH)2]+ observed at m/z=833 (40%) followed by
[LDepMn]+ (at m/z=416, 100%). The molecular structure of
complex 3 has been established by single-crystal X-ray dif-
fraction analysis (Figure 2). Compound 3 crystallizes in the
adduct A with 3 in THF at room temperature led to the for-
mation of manganese silathiocarboxylate 4 under release of
DMAP and dihydrogen gas (Scheme 3). Concentration of
the resulting solution and cooling to ꢀ208C gave complex 4
as yellow crystals in 91% yield.
Complex 4 represents the first transition-metal complex
of a heavier thiocarboxylate. Its composition has been con-
firmed by MS and elemental analysis. Its MS (EI) spectrum
revealed the molecular ion peak at m/z=909 (100%). The
compound is sparingly soluble in n-hexane, but soluble in di-
ethyl ether, toluene, and THF. As expected, it is paramag-
1
netic in the solution, as was indicated by H NMR, which
showed very broad signals. Magnetic measurements per-
formed for solution of 4 revealed a meff value of 5.3 mB at
room temperature, corresponding to a spin-only value of
five unpaired electrons (S=5/2).
A
single-crystal X-ray diffraction analysis revealed
a monomeric structure of 4 with three THF molecules in the
asymmetric unit in monoclinic space group C2/
a
c (Figure 3). As a thiocarboxylate analogue, the sulfur and
Figure 2. Molecular structure of 3. Thermal ellipsoids are drawn at 50%
probability level. Hydrogen atoms, except for those at Mn atoms, are
ꢀ
omitted for clarity. Selected bond lengths [ꢂ] and angles [8]: Mn1 N1
ꢀ
ꢀ
2.064(2), Mn1 N2 2.068(2), Mn1···Mn1’ 2.7464(7), Mn1 H1 1.86(2),
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
Mn1’ H1 1.87(2), N1 C2 1.328(2), C4 N2 1.331(3), C2 C3 1.403(3), C3
C4 1.403(3); N1-Mn1-N2 92.21(6), C2-N1-Mn1 124.2(1), C4-N2-Mn1
123.3(1), N2-C4-C3 124.9(2), N1-C2-C3 124.1(2), C2-C3-C4 129.6(2).
Symmetry transformations were used to generate equivalent atoms with
(’): ꢀx+1, ꢀy, ꢀz.
monoclinic space group P21/n and is a dimer formed by two
Mn-H-Mn three-center two-electron bonds. The conforma-
tion of the ring subunits in 3 is quite similar to that of 2,
except for the short distance between the two Mn centers
ꢀ
(2.7464(7) ꢂ). The latter Mn Mn distance is reminiscent of
that
observed
in
Mn
G
core
of
[({tBuN(ꢀ)SiMe2N(CH2CH2PiPr2)2}Mn)
CHTUNGTRENNUNG
2A(m-H)2]
(2.7945(7) ꢂ),[11] suggesting electronic unsaturation of the
Mn atoms.[12] The Mn H bond lengths (1.86(2) and
ꢀ
Figure 3. Molecular structure of 4. Thermal ellipsoids are drawn at 50%
probability level. Hydrogen atoms are omitted for clarity. Selected bond
ꢀ
1.87(2) ꢂ) of 3 are in the range of Mn H distances reported
ꢀ
ꢀ
ꢀ
previously.[11,12]
lengths [ꢂ] and angles [8]: Mn1 O1 2.070(3), Mn1 N4 2.112(4), Mn1 N3
ꢀ
ꢀ
ꢀ
2.114(4), Mn1 S1 2.536(1), Mn1···Si1 2.790(1), S1 Si1 2.058(2), Si1 O1
ꢀ
ꢀ
1.583(3), Si1 N2 1.805(4), Si1 N1 1.809(4); N4-Mn1-N3 89.7(1), O1-
Mn1-S1 79.27(8), Si1-S1-Mn1 73.94(5), N2-Si1-N1 96.7(2), O1-Si1-S1
108.0(1), Si1-O1-Mn1 98.7(1).
Synthesis of manganese silathiocarboxylate 4 and germa-
thiocarboxylate 5: Reaction of silathiocarboxylic acid
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M. Driess et al.
oxygen atoms of the Si(=S)O moiety coordinate to the man-
ganese center. Both manganese and silicon centers achieve
a distorted tetrahedral coordination sphere and feature
puckered six-membered C3N2M rings (M=Mn, Si). The
ꢀ
Mn N distances of 2.112(2) and 2.114(2) ꢂ are slightly elon-
gated compared with those observed in 2 and 3 (2.047(2)–
ꢀ
2.068(2) ꢂ). The Mn O bond length (2.070(3) ꢂ) is slightly
longer than respective values observed in [(LDipMn)
2A
OOCCH3)2] (1.991(7)–2.031(7) ꢂ).[7c] The Mn S distance
[2.536(1) ꢂ] is longer than the average value of Mn-
ꢀ
ACHTUNGTRENNUNG[(OPPh2)ACHTUNGTRENNUNG
(SPPh2)N]2 with a MnO2S2 core (2.447(1) ꢂ).[13]
ꢀ
The Si N distances of 1.805(4) and 1.809(4) ꢂ are similar
with those observed for precursor
A (1.809(2) and
1.827(2) ꢂ),[4i] whereas the Si O bond length in 4 is shorter
than that in precursor A (1.620(2) ꢂ). In contrast, the Si S
ꢀ
ꢀ
distance of 2.058(2) ꢂ in 4 is longer than the value in A
(1.993(1) ꢂ) due to larger p-electron resonance within the
Si-S-O carboxylic-like moiety. However, this value is still
ꢀ
Figure 4. Molecular structure of complex 5. Thermal ellipsoids are drawn
at 50% probability level. Hydrogen atoms are omitted for clarity. Select-
significantly shorter than
a normal Si S single bond
(ꢁ2.14 ꢂ).[14]
ꢀ
ꢀ
ed bond lengths [ꢂ] and angles [8]: Ge1 O1 1.722(2), Ge1 N2 1.922(3),
Similarly, metalation of germathiocarboxylic acid B[5a]
with 3 in THF at ambient temperature afforded the expect-
ed manganese(II) germathiocarboxylate 5 (Scheme 3). Due
to the dimer nature of B, the reaction is solvent dependent.
For example, in toluene solution, the reaction occurs very
slowly even after 12 h at room temperature. However, in
THF, the reaction proceeds quite fast and is completed after
12 h. After work-up, complex 5 was isolated as yellow crys-
tals in 90% yield. The solubility and magnetic property of 5
is similar to that of the silicon analogue 4. The solution mag-
netic susceptibility of 5 was found to be 5.6 mB, again sug-
gesting a high-spin manganese(II) species. Its MS (EI) spec-
trum revealed the molecular peak at m/z=955 (100%).
Complex 5 crystallizes readily from diethyl ether solutions
without co-crystallized solvent molecules, as was indicated
by X-ray diffraction analysis. However, the structure is dis-
ordered. Suitable single crystals without disordering of 5
could be obtained in toluene solution after two weeks at
ꢀ208C. Their X-ray analysis revealed that the compound
crystallizes in the monoclinic space group Pn (Figure 4). The
refined structure of 5 is akin to that of 4 with almost the
same features for the geometric parameter around the man-
ꢀ
ꢀ
ꢀ
ꢀ
Ge1 N1 1.925(3), Ge1 S1 2.1401(9), Mn1 O1 2.074(2), Mn1 N4
ꢀ
ꢀ
2.113(3), Mn1 N3 2.128(3), Mn1 S1 2.545(1), Mn···Ge 2.847 (2); N2-
Ge1-N1 94.8(1), O1-Ge1-S1 105.71(8), N4-Mn1-N3 90.1(1), O1-Mn1-S1
83.28(7), Ge1-S1-Mn1 74.28(3), Ge1-O1-Mn1 96.7(1).
color change from yellow to dark brown and formation of
a mixture of unidentified products. Interestingly, 4 and 5 me-
diate clean and mild stoichiometric oxygenation of Ph3P to
Ph3P=O in the presence of dioxygen. Further investigations
are needed to elucidate the nature of the respective Mn O2
complexes formed initially and the mechanism of oxygena-
tion of Ph3P.
ꢀ
Conclusion
The coordination chemistry of divalent manganese com-
plexes supported by silathiocarboxylate 4 and germathiocar-
boxylate 5 ligands is presented. Both complexes were readi-
ly obtained in high yield from reaction of silathiocarboxylic
adduct A and germathiocarboxylic acid B with nacnac man-
ganese hydride 3. The latter could be easily prepared from
the corresponding manganese bromide 2. Complexes 4 and
5 represent the first transition-metal sila- and germathiocar-
boxylates, respectively. The E=S (E=Si, Ge) bonds in 4 and
5 are stabilized by S!Mn and N!E dative interaction as
well as p-electron delocalization of the E(S)O moieties. Our
results showed that sila- and germathiocarboxylato ligands
can serve as competent supporting ligands for transition
metals. Preliminary experiments revealed that both com-
plexes are capable to activate dioxygen and oxygenate tri-
phenylphosphine into its oxide under mild conditions. The
synthesis of other redox-active transition-metal complexes
by using the Si(=S)O and Ge(=S)O carboxylate-like ligands
and their use for activation of small molecules is currently
in progress.
ꢀ
ganese center. The Ge N bond lengths (1.923(3) and
1.925(3) ꢂ) are comparable to those observed in the precur-
sor B (1.911(2) and 1.916(2) ꢂ).[5a] The shortening of the
ꢀ
Ge O distance (1.722(2) ꢂ in 5 vs. 1.751(2) ꢂ in B) and
ꢀ
elongation of the Ge S distance (2.1401(9) ꢂ in 5 versus
2.077(1) ꢂ in B) is reminiscent of those of 4 compared with
ꢀ
its precursor A. The Mn S distance of 2.545(1) ꢂ in 5 is
also similar to that found in 4 (2.536(1) ꢂ). The latter obser-
vation suggests the presence of p-electron delocalization
within the Ge-S-O moiety in 5.
Both manganese silathiocarboxylate 4 and germathiocar-
boxylate 5 are very sensitive towards air and moisture. Pre-
liminary experiments showed that 4 and 5 are capable to ac-
tivate dioxygen under mild condition. Thus, reactions of 4
and 5 with dry dioxygen in toluene led to an immediate
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Metalation of Silicon and Germanium Analogues of Thiocarboxylic Acids
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Syntheses of 3: To a solution of 2 (3.61 g, 3.64 mmol) in toluene (50 mL)
was added a solution of KBEt3H (7.3 mL, 1m in THF, 7.28 mmol) by sy-
ringe at RT. After stirring for 3 h, volatiles were removed in vacuo. The
residue was extracted with toluene (80 mL). The concentrated reaction
solution (ca. 20 mL) was chilled to ꢀ208C for 24 h, affording yellow crys-
tals of 3 suitable for X-ray diffraction analysis (yield: 2.22 g, 2.66 mmol,
73%). M.p. 2328C (decomp); IR (KBr): 674 (w), 761 (m), 801 (w), 851
(w), 1022 (w), 1106 (w), 1181 (w), 1267(w), 1329 (w), 1397 (s), 1445 (s),
1524 (s), 2873 (m), 2931 (m), 2961 (m), 3062 cmꢀ1 (w); meff (Evans, C6D6):
5.0 mB; cryoscopic measurement (C6H6): M=604 gmolꢀ1 (dimer: M=835
and monomer 417 gmolꢀ1; both might exist in the solution); MS (EI): m/
z (%): 833 (40) [M]+, 416 (100) [LDepMn]+; elemental analysis calcd (%)
for C50H68N4Mn2 (834.99): C 71.92, H 8.21, N 6.71; found: C 71.30, H
8.41, N 7.07.
Experimental Section
General: All experiments and manipulations were carried out under dry
oxygen-free nitrogen by using standard Schlenk techniques or in an
MBraun inert atmosphere dry box with an atmosphere of purified nitro-
gen. Solvents were dried by standard methods and freshly distilled prior
use. The starting material 1,[15] silathiocarboxylic acid DMAP adduct A,[4i]
and germathiocarboxylic acid B[5a] were prepared according to literature
procedures. KBEt3H (1m in THF) was purchased from Aldrich. MS (EI)
spectra were recorded on a Finnigan MAT 955 instrument. The solution
magnetic susceptibility values were determined by using the solution
Evans method[9] in C6D6 at RT. The IR spectra were recorded on a Nico-
let Magna 750 spectrometer with nitrogen gas purge. Elemental analyses
were performed on a FlashEA 1112 CHNS analyzer.
Syntheses of 4: To a solution of A (0.31 g, 0.50 mmol) in THF (10 mL)
was added a solution of 3 (0.21 g, 0.25 mmol) in THF (8 mL) at RT.
After stirring for 10 min, the volume of the resulting solution was con-
centrated to about 5 mL under reduced pressure. The concentrated reac-
tion solution was chilled to ꢀ208C for 24 h, affording yellow crystals of 4
(yield: 0.41 g, 0.46 mmol, 91%). M.p. 2368C (decomp); IR (KBr): 434
(w), 463 (w), 548 (w), 590 (w), 615 (m), 659 (m), 762 (m), 778 (w), 802
(m), 848 (w), 895 (w), 934 (w), 1001 (m), 1025 (m), 1058 (w), 1105 (w),
1179 (m), 1267 (m), 1321 (m), 1393 (s), 1442 (s), 1523 (s), 1552 (s), 2868
(m), 2929 (m), 2963 (m), 3060 cmꢀ1 (w); meff (Evans, C6D6): 5.3 mB; MS
(EI): m/z (%): 909 (100) [M]+; elemental analysis calcd (%) for
C54H74N4MnSiSO (910.29): C 71.25, H 8.19, N 6.15; found: C 70.82, H
8.17, N 6.27.
Single-crystal X-ray structure determination: Each crystal was mounted
on a glass capillary in perfluorinated oil and measured in a cold N2 flow.
The data of 2, 3, 4, and 5 were collected on an Oxford Diffraction Xcali-
bur S Sapphire at 150 K (MoKa radiation, l=0.71073 ꢂ). The structures
were solved by direct methods and refined on F2 with the SHELX-97[16]
software package. The positions of the H atoms were calculated and con-
sidered isotropically according to a riding model. CCDC-876620 (2),
CCDC-876621 (3), CCDC-876622 (4), and CCDC-876623 (5) contain the
supplementary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
Compound 2: Monoclinic; space group P21/n; a=13.2014(3), b=
10.6285(2), c=17.6446(3) ꢂ; b=101.430(2)8; V=2426.63(8) ꢂ3; Z=4;
Syntheses of 5: To a solution of B (0.27 g, 0.50 mmol) in THF (10 mL)
was added a solution of 3 (0.21 g, 0.25 mmol) in THF (8 mL) at RT.
After stirring for 12 h, volatiles were removed in vacuo and the residue
was extracted with toluene (10 mL). The concentrated reaction solution
was chilled to ꢀ208C for one week, affording yellow crystals of 5 (yield:
0.43 g, 0.45 mmol, 90%). M.p. 2518C (decomp); IR (KBr): 419 (m), 466
(m), 537 (w), 592 (w), 642 (w), 761 (m), 778 (m), 803 (m), 848 (w), 872
(w), 934 (w), 1023 (m), 1058 (w), 1104 (w), 1178 (m), 1262 (m), 1325 (m),
1396 (s), 1452 (s), 1526 (s), 1543 (s), 2867 (m), 2927 (m), 2967 (m),
3060 cmꢀ1 (w); meff (Evans, C6D6): 5.6 mB; MS (EI): m/z (%): 955 (100)
[M]+; elemental analysis calcd (%) for C54H74N4MnGeSO (954.79): C
67.93, H 7.81, N 5.87; found: C 67.72, H 7.69, N 6.20.
ACHTUNGTRENNUNG
1calc =1.359 mgmꢀ3; m(MoKa)=2.203 mmꢀ1; 17819 collected reflections;
4265 crystallographically independent reflections [Rint =0.0338]; 3326 re-
flections with [I>2s(l)]; qmax =25.008; R(Fo)=0.0271 [I>2s(l)];
2
wR
N
Compound 3: Monoclinic; space group P21/n; a=13.366(1), b=
12.1017(9), c=15.334(1) ꢂ; b=110.69(1); V=2320.4(3) ꢂ3; Z=2; 1calc
1.195 mgmꢀ3; m(MoKa)=0.581 mmꢀ1; 18030 collected reflections; 4079
crystallographically independent reflections [Rint =0.0461]; 3588 reflec-
=
ACHTUNGTRENNUNG
2
tions with [I>2s(l)]; qmax =258; R(Fo)=0.0360 [I>2s(l)]; wRACTHNUTRGEN(UNG Fo )=
0.0830 (all data); 262 refined parameters.
Compound 4: Monoclinic; space group C2/c; a=22.5724(9), b=
13.5902(7), c=40.703(2) ꢂ; b=93.6009(4); V=12461.3(9) ꢂ3; Z=4;
Reactivity investigation. Reaction with dioxygen: Compound 4 or 5
(0.03 mmol) was dissolved in toluene at RT. The color of the solution
changed immediately from yellow to brown, when dry dioxygen was in-
troduced in the solution. After stirring for 10 min at RT, a brown precipi-
tate was observed. 1H NMR spectra of the reaction mixture showed
a large amount of free ligand, LDipH and LDepH. Addition of triphenyl
phosphine to the resulted mixture did not lead to significant conversion
of triphenyl phosphine to triphenylphosphine oxide.
ACHTUNGTRENNUNG
1calc =1.047 mgmꢀ3; m(MoKa)=0.303 mmꢀ1; 30355 collected reflections;
10561 crystallographically independent reflections [Rint =0.0687]; 7338
2
reflections with [I>2s(l)]; qmax =258; R(Fo)=0.0845 [I>2s(l)]; wR
0.2129 (all data); 641 refined parameters.
Compound 5: Monoclinic; space group Pn; a=13.5314(3), b=12.4916(3),
c=19.7563(5) ꢂ; b=107.446(3)8; V=3185.8(1) ꢂ3; Z=2; 1calc
0.995 mgmꢀ3; m(MoKa)=0.735 mmꢀ1; 26521 collected reflections; 8345
crystallographically independent reflections [Rint =0.0291]; 8036 reflec-
ACHTUNGRTEN(NUNG Fo )=
=
ACHTUNGTRENNUNG
Reaction with dioxygen in the presence of triphenyl phosphine: Com-
pound 4 or 5 (0.03 mmol) was dissolved in toluene under N2 and triphen-
yl phosphine (2 equiv) was added. An immediate color change occurred
upon exchange of the N2 to dry dioxygen, and the initial yellow solution
2
tions with [I>2s(l)], qmax =258; R(Fo)=0.0368 [I>2s(l)]; wRACTHNUTRGEN(UNG Fo )=
0.0987 (all data); 575 refined parameters.
Syntheses of 2: To a solution of 1 (18.8 g, 51.9 mmol) in diethyl ether
(180 mL) was added a solution of nBuLi (32.4 mL, 1.6m in n-hexane,
51.9 mmol) by syringe with stirring at ꢀ308C. The reaction solution was
allowed to warm to RT and stirred for 3 h. To the resulting solution,
a solid of MnBr2 (11.13 g, 51.9 mmol) was added, and the reaction mix-
ture was stirred further for 12 h at RT. Volatiles were removed in vacuo,
the residue extracted with n-hexane (3ꢃ80 mL). Subsequently, the con-
centrated reaction solution (ca. 100 mL) was chilled to ꢀ208C for 48 h,
affording yellow crystals of 2 suitable for X-ray diffraction analysis
(yield: 22.1 g, 22.3 mmol, 86%). M.p. 2438C (decomp); IR (KBr): 521
(w), 630 (w), 757 (m), 804 (m), 852 (w), 934 (w), 1024 (w), 1108(w), 1178
(m), 1266 (m), 1324 (m), 1390 (s), 1442 (s), 1521 (s), 1541 (s), 2877 (m),
2934 (m), 2967 (m), 3061 cmꢀ1 (w); meff (Evans, C6D6): 7.2 mB; cryoscopic
measurement (C6H6): M=732 gmolꢀ1 (dimer: M=993 and monomer
497 gmolꢀ1; both might exist in the solution); MS (EI): m/z (%): 497 (90)
[LDepMnBr]+, 416 (100) [LDepMn]+; elemental analysis calcd (%) for
C50H66N4Mn2Br2 (992.78): C 60.49, H 6.70, N 5.64; found: C 59.92, H
6.52, N 4.53.
1
turned brown. After stirring for 24 h at RT, H NMR spectra of the reac-
tion mixture showed that a large amount of free ligand LDipH and LDep
H
were formed. Volatiles were removed under reduced pressure. The result-
ing brown residue was dissolved in CH2Cl2 and passed through a thin
silica pad (to remove the manganese complex), which was washed with
ethyl acetate. The volatiles in the filtrates were removed under vacuum,
and the resulting residue was characterized with 1H and 31P NMR spec-
troscopy and MS (LC-ESI). In both cases, one equivalent of the triphenyl
phosphine was converted to triphenylphosphine oxide. The same experi-
ment with 18O2 (97%) resulted in the formation of 18O-labeled Ph3P=O
in 97% yield.
Chem. Eur. J. 2012, 00, 0 – 0
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
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M. Driess et al.
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Acknowledgements
Financial support from the Cluster of Excellence “Unifying Concepts in
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Received: April 19, 2012
Revised: June 6, 2012
Published online: && &&, 0000
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ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
ÝÝ
These are not the final page numbers!

Metalation of Silicon and Germanium Analogues of Thiocarboxylic Acids
FULL PAPER
Transition-Metal Complexes
S. Yao, Y. Xiong, M. Driess* &&&& — &&&&
Facile Metalation of Silicon and
Germanium Analogues of Thiocarbox-
ylic Acids with Manganese(II) Hydride
Precursor
Active guys: The first transition-metal
sila- and germathiocarboxylates were
obtained by facile metalation of the
corresponding heavier thiocarboxylic
acids with currently unknown b-diketi-
minato manganese hydride. Prelimi-
nary investigations revealed that these
complexes are capable to activate
dioxygen and to oxygenate triphenyl-
phosphane at ambient temperature
(see scheme).
Chem. Eur. J. 2012, 00, 0 – 0
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
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These are not the final page numbers!