Preparation and reactivity of stannyl complexes of manganese and rhenium

Article abstract of DOI:10.1021/om070220m

The trichlorostannyl complexes M(SnCl₃)(CO)_nP _5-n (1-3: M = Mn, Re; P = PPh(OEt)₂ (a), P(OEt) ₃ (b); n = 2, 3) were prepared by allowing chloro MCl(CO) _nP_5-n compounds to react w

Full text of DOI:10.1021/om070220m

2918
Organometallics 2007, 26, 2918-2930
Preparation and Reactivity of Stannyl Complexes of Manganese and
Rhenium
Gabriele Albertin,*,† Stefano Antoniutti,† Jesu´s Castro,‡ Soledad Garc´ıa-Fonta´n,‡ and
Gianluigi Zanardo†
Dipartimento di Chimica, UniVersita` Ca’ Foscari di Venezia, Dorsoduro 2137, 30123 Venezia, Italy, and
Departamento de Qu´ımica Inorga´nica, Facultade de Qu´ımica, Edificio de Ciencias Experimentais,
UniVersidade de Vigo, 36310 Vigo (Galicia), Spain
ReceiVed March 8, 2007
The trichlorostannyl complexes M(SnCl3)(CO)nP5-n (1-3: M ) Mn, Re; P ) PPh(OEt)2 (a), P(OEt)3
(b); n ) 2, 3) were prepared by allowing chloro MCl(CO)nP5-n compounds to react with an excess of
SnCl2‚2H2O. Treatment of compounds 1-3 with NaBH4 in ethanol yielded the tin polyhydride derivatives
M(SnH3)(CO)nP5-n (4-6). Treatment of 1-3 with MgBrMe gave the trimethylstannyl complexes
M(SnMe3)(CO)nP5-n (7-9), and the reaction of 1-3 with MgBr(CtCH) yielded the trialkynylstannyl
derivatives M[Sn(CtCH)3](CO)nP5-n (10, 11). The alkynylstannyl complexes M[Sn(CtCR)3](CO)nP5-n
(12-14: R ) p-tolyl) were also prepared by allowing M(SnCl3)(CO)nP5-n compounds to react with
Li+[CtCR]- in thf. The complexes were characterized by spectroscopy and by X-ray crystal structure
determinations of 4a, 6b, and 9b. Reaction of the tin trihydride complexes Re(SnH3)(CO)2P3 (6) with
CO2 (1 atm) led to the binuclear OH-bridging bis(formate) derivatives [Re{Sn[OC(H)dO]2(µ-OH)}-
(CO)2P3]2 (15). A reaction path for the formation of 15, involving the tin hydride bis(formate) intermediate
Re[SnH{OC(H)dO}2](CO)2P3, is discussed. The X-ray crystal structure of 15b is reported.
Reactivity studies have also highlighted interesting properties
of [Os]-SnH3 compounds, including the hydridic nature of the
SnH3 group.
These results prompted us to extend our study of hydride-
stannyl complexes to other transition metals, with the aim of
Introduction
The chemistry of transition-metal stannyl complexes has been
extensively developed in recent years,1,2 both because there has
been a variety of reactions shown and because the introduction
of a tin ligand into the metal fragment often modifies the nature
of noble-metal catalysts.1-3
(2) (a) Buil, M. L.; Esteruelas, M. A.; Lahoz, F. J.; On˜ate, E.; Oro, L.
A. J. Am. Chem. Soc. 1995, 117, 3619-3620. (b) Nakazawa, H.;
Yamaguchi, Y.; Miyoshi, K. Organometallics 1996, 15, 1337-1339. (c)
Schubert, U.; Grubert, S. Organometallics 1996, 15, 4707-4713. (d) Akita,
M.; Hua, R.; Nakanishi, S.; Tanaka, M.; Moro-oka, Y. Organometallics
1997, 16, 5572-5584. (e) Djukic, J.-P.; Do¨tz, K. H.; Pfeffer, M.; De Cian,
A.; Fischer, J. Organometallics 1997, 16, 5171-5182. (f) Nakazawa, H.;
Yamaguchi, Y.; Kawamura, K.; Miyoshi, K. Organometallics 1997, 16,
4626-4635. (g) Biswas, B.; Sugimoto, M.; Sakaki, S. Organometallics
1999, 18, 4015-4026. (h) Baya, M.; Crochet, P.; Esteruelas, M. A.;
Gutierrez-Puebla, E.; Ruiz, N. Organometallics 1999, 18, 5034-5043. (i)
Rickard, C. E. F.; Roper, W. R.; Woodman, T. J.; Wright, L. J. Chem.
Commun. 1999, 837-838. (j) Adams, H.; Broughton, S. G.; Walters, S. J.;
Winter, M. J. Chem. Commun. 1999, 1231-1232. (k) Clark, A. M.; Rickard,
C. E. F.; Roper, W. R.; Woodman, T. J.; Wright, L. J. Organometallics
2000, 19, 1766-1774. (l) Hermans, S.; Johnson, B. F. G. Chem. Commun.
2000, 1955-1956. (m) Turki, M.; Daniel, C.; Za´lis, S.; Vlcˆek, A., Jr.; van
Slageren, J.; Stufkens, D. J. J. Am. Chem. Soc. 2001, 123, 11431-11440.
(n) Neale, N. R.; Tilley, T. D. J. Am. Chem. Soc. 2002, 124, 3802-3803.
(o) Esteruelas, M. A.; Lledos, A.; Maseras, F.; Oliva´n, M.; On˜ate, E.; Tajada,
M. A.; Toma`s, J. Organometallics 2003, 22, 2087-2096. (p) Adams, R.
D.; Captain, B.; Smith, J. L., Jr.; Hall, M. B.; Beddie, C. L.; Webster, C.
E. Inorg. Chem. 2004, 43, 7576-7578. (q) Neale, N. R.; Tilley, T. D. J.
Am. Chem. Soc. 2005, 127, 14745-14755. (r) Adams, R. D.; Captain, B.;
Herber, R. H.; Johansson, M.; Nowik, I.; Smith, J. L.; Smith, M. D. Inorg.
Chem. 2005, 44, 6346-6358. (s) Sagawa, T.; Ohtsuki, K.; Ishiyama, T.;
Ozawa, F. Organometallics 2005, 24, 1670-1677. (t) Adams, R. D.;
Captain, B.; Hollandsworth, C. B.; Johansson, M.; Smith, J. L., Jr.
Organometallics 2006, 25, 3848-3855.
Tin ligands may, in fact, modify the properties of complexes,
both having a strong labilizing effect on their trans ligands and
being quite labile themselves, and thus providing vacant
coordination sites on transition metals by dissociation. In
addition, the ease of oxidative addition and subsequent reductive
elimination of tin(IV) compounds may strongly influence the
catalytic cycle of processes involving stannyl derivatives.1,3
Numerous mono- and polynuclear stannyl complexes of
transition metals containing several organostannyl (SnR3) or
halogenostannyl ligands (SnX3) have been synthesized. How-
ever, despite numerous studies, no examples of stable complexes
containing the simplest of the tin ligands, the trihydride SnH3,
have ever been reported. In a recent study,4 we demonstrated
that tin trihydride complexes can in fact be prepared using a
osmium(II) fragment of the type Os(Tp)L(PPh3) (Tp ) tris-
(pyrazolyl)borate; L ) phosphite) to stabilize the SnH3 ligand.
* To whom correspondence should be addressed. Fax: +39 041 234
8917. E-mail: albertin@unive.it.
† Universita` Ca’ Foscari.
‡ Universidade de Vigo.
(1) (a) Mackay, K. M.; Nicholson, B. K. In ComprehensiVe Organome-
tallic Chemistry; Wilkinson, G., Stone, F. G. A., Abel, E. W., Eds.;
Pergamon Press: New York, 1982; Vol. 2, pp 1043-1114. (b) Holt, M.
S.; Wilson, W. L.; Nelson, J. H. Chem. ReV. 1989, 89, 11-49. (c) Lappert,
M. F.; Rowe, R. S. Coord. Chem. ReV. 1990, 100, 267-292. (d) Davies,
A. G. In ComprehensiVe Organometallic Chemistry; Stone, F. G. A., Abel,
E. W., Wilkinson, G., Eds.; Pergamon Press: New York, 1995; Vol. 2, pp
218-297. (e) Davies, A. G. Organotin Chemistry; Wiley-VCH: Weinheim,
Germany, 2004.
(3) (a) Coupe´, J. N.; Jorda˜o, E.; Fraga, M. A.; Mendes, M. J. Appl. Catal.
A. 2000, 199, 45. (b) Hermans, S.; Raja, R.; Thomas, J. M.; Johnson, B. F.
G.; Sankar, G.; Gleeson, D. Angew. Chem., Int. Ed. 2001, 40, 1211. (c)
Huber, G. W.; Shabaker, J. W.; Dumesic, J. A. Science 2003, 300, 2075.
(d) Adams, R. D.; Captain, B.; Johansson, M.; Smith, J. L., Jr. J. Am. Chem.
Soc. 2005, 127, 488-489.
(4) Albertin, G.; Antoniutti, S.; Bacchi, A.; Bortoluzzi, M.; Pelizzi, G.;
Zanardo, G. Organometallics 2006, 25, 4235-4237.
10.1021/om070220m CCC: $37.00 © 2007 American Chemical Society
Publication on Web 04/19/2007

Stannyl Complexes of Mn and Re
Organometallics, Vol. 26, No. 11, 2007 2919
otherwise noted. 1H and 13C spectra are referred to internal
tetramethylsilane; 31P{1H} chemical shifts are reported with respect
to 85% H3PO4 and those of 119Sn with respect to Sn(CH3)4, and in
both cases downfield shifts are considered positive. COSY, HMQC,
and HMBC NMR experiments were performed with standard
programs. The SwaN-MR and iNMR software packages9 were used
to treat NMR data. The conductivities of 10-3 mol dm-3 solutions
of the complexes in CH3NO2 at 25 °C were measured on a
Radiometer CDM 83 instrument. Elemental analyses were deter-
mined by the Microanalytical Laboratory of the Dipartimento di
Scienze Farmaceutiche, University of Padova, Padova, Italy.
Synthesis of Complexes. The pentacarbonyl complexes MnX-
(CO)5 and ReX(CO)5 (X ) Cl, Br) and hydride complexes
ReH(CO)nP5-n (n ) 2, 3; P ) PPh(OEt)2, P(OEt)3) were prepared
following previously reported methods.5c,10
testing both whether tin trihydride complexes can be prepared
for other metals and how the properties of the stannyl group
are influenced by the metal fragment. We focused our attention
on d6 manganese(I) and rhenium(I) central metals;5 these are
isoelectronic with Os(II), and their tin chemistry is much less
developed than that of other d6 complexes.1,6,7
The results of these studies, which include the preparation
and reactivity of the first tin trihydride complexes of manganese
and rhenium, are reported here.
Experimental Section
General Comments. All synthetic work was carried out under
an appropriate atmosphere (Ar, N2) using standard Schlenk
techniques or an inert-atmosphere drybox. Once isolated, the
complexes were found to be relatively stable in air but were stored
under nitrogen at -25 °C. All solvents were dried over appropriate
drying agents, degassed on a vacuum line, and distilled into vacuum-
tight storage flasks. Mn2(CO)10 and Re2(CO)10 were Pressure
Chemical Co. (USA) products, used as received. The phosphite
PPh(OEt)2 was prepared by the method of Rabinowitz and Pellon.8
The reagents MgBrMe (3 M solution in diethyl ether) and MgBr-
(CtCH) (2.5 M solution in diethyl ether) were Aldrich products,
used as received. The lithium acetylide Li+CtCR- (R ) p-tolyl)
was prepared by reacting a slight excess of the appropriate acetylene
(35 mmol) with lithium (30 mmol, 0.21 g) in 20 mL of tetrahy-
drofuran (thf). Other reagents were purchased from commercial
sources in the highest available purity and used as received. Infrared
spectra were recorded on a Nicolet Magna 750 or Perkin-Elmer
Spectrum-One FT-IR spectrophotometer. NMR spectra (1H, 31P,
13C, 119Sn) were obtained on an AC200 or AVANCE 300 Bruker
spectrometer at temperatures between -90 and +30 °C, unless
MnX(CO)3[PPh(OEt)2]2 (X ) Cl, Br). An excess of PPh(OEt)2
(14.6 mmol, 2.9 mL) was added to a solution of the appropriate
MnX(CO)5 complex (5.82 mmol) in toluene (X ) Cl) or benzene
(X ) Br), and the reaction mixture was refluxed for 2 h. The solvent
was removed under reduced pressure to give a brown oil, which
was triturated with ethanol (5 mL). A yellow (X ) Cl) or orange
(X ) Br) solid slowly separated out from the resulting solution,
which was isolated by filtration and crystallized from CH2Cl2 and
ethanol; yield g90%.
MnCl(CO)3[PPh(OEt)2]2. IR (KBr; cm-1): νCO 2045 (w), 1981,
1
1910 (s). H NMR (CD2Cl2, 25 °C; δ): 7.70, 7.43 (m, 10 H, Ph),
4.20, 3.98 (m, 8 H, CH2), 1.33 (t, 12 H, CH3). 31P{1H} NMR (CD2-
Cl2, 25 °C; δ): 183.1 (s, br). Anal. Calcd for C23H30ClMnO7P2:
C, 48.40; H, 5.30; Cl, 6.21. Found: C, 48.52; H, 5.25; Cl, 6.43.
MnBr(CO)3[PPh(OEt)2]2. IR (KBr; cm-1): νCO 2051 (w), 1976,
1
1906 (s). H NMR (CD2Cl2, 25 °C; δ): 7.70, 7.46 (m, 10 H, Ph),
4.19, 3.95 (m, 8 H, CH2), 1.34 (t, 12 H, CH3). 31P{1H} NMR (CD2-
Cl2, -70 °C; δ): A2, 185.2 (s). Anal. Calcd for C23H30BrMnO7P2:
C, 44.90; H, 4.91; Br, 12.99. Found: C, 44.77; H, 4.93; Br, 12.80.
ReX(CO)3[PPh(OEt)2]2 (X ) Cl, Br). These complexes were
prepared like the related MnX(CO)3[PPh(OEt)2]2 complexes, using
a reaction time of 2.5 h; yield g80%.
(5) For our previous papers on Mn and Re complexes stabilized by
phosphite ligands, see: (a) Albertin, G.; Antoniutti, S.; Bacchi, A.;
Bordignon, E.; Busatto, F.; Pelizzi, G. Inorg. Chem. 1997, 36, 1296-1305.
(b) Albertin, G.; Antoniutti, S.; Bettiol, M.; Bordignon, E.; Busatto, F.
Organometallics 1997, 16, 4959-4969. (c) Albertin, G.; Antoniutti, S.;
Garcia-Fonta´n, S.; Carballo, R.; Padoan, F. J. Chem. Soc., Dalton Trans.
1998, 2071-2081. (d) Albertin, G.; Antoniutti, S.; Bacchi, A.; Ballico, G.
B.; Bordignon, E.; Pelizzi, G.; Ranieri, M.; Ugo, P. Inorg. Chem. 2000,
39, 3265-3279. (e) Albertin, G.; Antoniutti, S.; Bacchi, A.; Bordignon,
E.; Miani, F.; Pelizzi, G. Inorg. Chem. 2000, 39, 3283-3293. (f) Albertin,
G.; Antoniutti, S.; Bordignon, E.; Visentin, E. Inorg. Chem. 2001, 40, 5465-
5467. (g) Albertin, G.; Antoniutti, S.; Bacchi, A.; Bordignon, E.; Giorgi,
M. T.; Pelizzi, G. Angew. Chem., Int. Ed. 2002, 41, 2192-2194. (h) Albertin,
G.; Antoniutti, S.; Bravo, J.; Castro, J.; Garcia-Fonta´n, S.; Mar´ın, M. C.;
Noe`, M. Eur. J. Inorg. Chem. 2006, 3451-3462.
(6) For manganese tin complexes, see: (a) Thompson, J. A. J.; Graham,
W. A. G. Inorg. Chem. 1967, 10, 1875-1879. (b) Clark, H. C.; Hunter, B.
K. J. Organomet. Chem. 1971, 31, 227-232. (c) Collman, J. P.; Hoyano,
J. K.; Murphy, D. W. J. Am. Chem. Soc. 1973, 95, 3424-3425. (d) Spek,
A. L.; Bos, K. D.; Bulten, E. J.; Noltes, J. G. Inorg. Chem. 1976, 15, 339-
345. (e) Chipperfield, J. R.; Hayter, A. C.; Webster, D. E. J. Chem. Soc.,
Dalton Trans. 1977, 485-490. (f) McCullen, S. B.; Brown, T. L. J. Am.
Chem. Soc. 1982, 104, 7496-7500. (g) Foster, S. P.; Mackay, K. M. J.
Organomet. Chem. 1983, 247, 21-26. (h) Bullock, J. P.; Palazzotto, M.
C.; Mann, K. R. Inorg. Chem. 1990, 29, 4413-4421. (i) Sullivan, R. J.;
Brown, T. L. J. Am. Chem. Soc. 1991, 113, 9155-9161. (j) Utz, T. L.;
Leach, P. A.; Geib, S. J.; Cooper, N. J. Chem. Commun. 1997, 847-848.
(k) Chen, Y.-S.; Ellis, J. E. Inorg. Chim. Acta 2000, 300-302, 675-682.
(l) Christendat, D.; Wharf, I.; Lebuis, A.-M.; Butler, I. S.; Gilson, D. F. G.
Inorg. Chim. Acta 2002, 329, 36-44.
ReCl(CO)3[PPh(OEt)2]2. IR (KBr; cm-1): νCO 2030 (m), 1974,
1
1895 (s). H NMR (CD2Cl2, 25 °C; δ): 7.70, 7.46 (m, 10 H, Ph),
4.15, 3.95 (m, 8 H, CH2), 1.35 (t, 12 H, CH3). 31P{1H} NMR (CD2-
Cl2, 25 °C; δ): A2, 130.0 (s). Anal. Calcd for C23H30ClO7P2Re:
C, 39.35; H, 4.31; Cl, 5.05. Found: C, 39.26; H, 4.39; Cl, 4.88.
ReBr(CO)3[PPh(OEt)2]2. IR (KBr; cm-1): νCO 2025 (w), 1978,
1
1893 (s). H NMR (CD2Cl2, 25 °C; δ): 7.70, 7.48 (m, 10 H, Ph),
4.12, 3.88 (m, 8 H, CH2), 1.33, 1.31 (t, 12 H, CH3). 31P{1H} NMR
(C6D6, 25 °C; δ): A2, 126.0 (s). Anal. Calcd for C23H30BrO7P2Re:
C, 37.00; H, 4.05; Br, 10.70. Found: C, 37.13; H, 4.00; Br, 10.91.
ReCl(CO)2P3 (P ) PPh(OEt)2, P(OEt)3). An excess of the
appropriate phosphite (17 mmol) was added to a solution of ReCl-
(CO)5 (5.0 mmol, 1.8 g) in 40 mL of toluene, and the reaction
mixture was irradiated at room temperature for 70 min in a Pyrex
Schlenk flask under a standard 400 W medium-pressure mercury
arc lamp. The solvent was then evaporated to dryness under reduced
pressure to give an oil, which was triturated with ethanol. A white
solid slowly separated out from the resulting solution, which was
isolated by filtration and crystallized from CH2Cl2 and ethanol; yield
g75%.
ReCl(CO)2[PPh(OEt)2]3. IR (KBr; cm-1): νCO 1985, 1873 (s).
1H NMR (CD2Cl2, 25 °C; δ): 7.75-7.30 (m, 15 H, Ph), 4.10, 3.75
(m, 12 H, CH2), 1.27, 1.23 (t, 18 H, CH3). 31P{1H} NMR (CD2Cl2,
25 °C; δ): AB2, δA 129.9, δB 127.8, JAB ) 35.5 Hz. Anal. Calcd
(7) For rhenium tin complexes see: (a) Preut, H.; Haupt, H.-J.; Florke,
U. Acta. Crystallogr., Sect. C 1984, 40, 600. (b) Haupt, H.-J.; Balsaa, P.;
Schwab, B.; Florke, U.; Preut, H. Z. Anorg. Allg. Chem. 1984, 22, 513. (c)
Narayanan, B. A.; Kochi, J. K. Inorg. Chim. Acta 1986, 122, 85-90. (d)
Westerberg, D. E.; Sutherland, B. E.; Huffman, J. C.; Caulton, K. G. J.
Am. Chem. Soc. 1988, 110, 1642-1643. (e) Warnock, G. F. P.; Moodie, L.
C.; Ellis, J. E. J. Am. Chem. Soc. 1989, 111, 2131-2141. (f) Luong, J. C.;
Faltynek, R. A.; Wrighton, M. S. J. Am. Chem. Soc. 1980, 102, 7892-
7900. (g) Huie, B. T.; Kirtley, S. W.; Knobler, C. B.; Kaesz, H. D. J.
Organomet. Chem. 1981, 213, 45-62. (h) Loza, M. L.; Crabtree, R. H.
Inorg. Chim. Acta 1995, 236, 63-66.
(9) Balacco, G. J. Chem. Inf. Comput. Sci. 1994, 34, 1235-1241 (http://
www.inmr.net/).
(10) (a) Reimer, K. J.; Shaver, A. Inorg. Synth. 1990, 28, 155-156, 158-
159. (b) Quick, M. H.; Angelici, R. J. Inorg. Synth. 1990, 28, 156-157.
(c) Schmidt, S. P.; Trogler, W. C.; Basolo, F. Inorg. Synth. 1990, 28, 160-
163.
(8) Rabinowitz, R.; Pellon, J. J. Org. Chem. 1961, 26, 4623-4626.

2920 Organometallics, Vol. 26, No. 11, 2007
Albertin et al.
for C32H45ClO8P3Re: C, 44.06; H, 5.20; Cl, 4.06. Found: C, 43.89;
H, 5.15; Cl, 4.23.
-129.7, JAM ) 251.0 Hz. 31P{1H} NMR (CD2Cl2, 25 °C; δ): A2,
117Sn
δA 131.0 (JA
) 243.0). Anal. Calcd for C23H30Cl3O7P2ReSn:
ReCl(CO)2[P(OEt)3]3. IR (KBr; cm-1): νCO 1980, 1969 (s). 1H
NMR (CD2Cl2, 25 °C; δ): 4.08 (m, 18 H, CH2), 1.30, 1.28 (t, 27
H, CH3). 31P{1H} NMR (CD2Cl2, 25 °C; δ): 115 (s, br). 31P{1H}
NMR (CD2Cl2, -70 °C; δ): AB2, δA 117.9, δB 117.2, JAB ) 46.8
Hz. Anal. Calcd for C20H45ClO11P3Re: C, 30.95; H, 5.84; Cl, 4.57.
Found: C, 31.17; H, 5.79; Cl, 4.44.
ReBr(CO)2P3 (P ) PPh(OEt)2, P(OEt)3). An excess of the
appropriate phosphite (20 mmol) was added to a solution of ReBr-
(CO)5 (5.0 mmol, 2.0 g) in 80 mL of toluene, and the reaction
mixture was refluxed for 2.5 h. The solvent was removed under
reduced pressure to give an oil, which was triturated with ethanol.
A white solid slowly separated out from the resulting solution,
which was isolated by filtration and crystallized from CH2Cl2 and
ethanol; yield g90%.
ReBr(CO)2[PPh(OEt)2]3. IR (KBr; cm-1): νCO 1981, 1870 (s).
1H NMR (CD2Cl2, 25 °C; δ): 7.75-7.30 (m, 15 H, Ph), 4.06, 3.74
(m, 12 H, CH2), 1.26, 1.23 (t, 18 H, CH3). 31P{1H} NMR (CD2Cl2,
25 °C; δ): AB2, δA 130.6, δB 128.2, JAB ) 35.6 Hz. Anal. Calcd
for C32H45BrO8P3Re: C, 41.93; H, 4.95; Br, 8.72. Found: C, 41.72;
H, 5.04; Br, 8.65.
ReBr(CO)2[P(OEt)3]3. IR (KBr; cm-1): νCO 1983, 1872 (s). 1H
NMR (CD2Cl2, 25 °C; δ): 4.10 (m, 18 H, CH2), 1.29, 1.27 (t, 27
H, CH3). 31P{1H} NMR (CD2Cl2, 25 °C; δ): 114 (s, br). 31P{1H}
NMR (CD2Cl2, -70 °C; δ): AB2, δA 117.4, δB 117.0, JAB ) 46.7
Hz. Anal. Calcd for C20H45BrO11P3Re: C, 29.27; H, 5.53; Br, 9.74.
Found: C, 29.36; H, 5.40; Br, 9.98.
Mn(SnCl3)(CO)3[PPh(OEt)2]2 (1a). In a 100 mL three-necked
round-bottomed flask were placed solid samples of MnCl(CO)3-
[PPh(OEt)2]2 (2.0 g, 3.0 mmol), an excess of SnCl2‚2H2O (9 mmol,
2.03 g), and 40 mL of ethanol. The reaction mixture was refluxed
for 2 h, and the solution was then evaporated under reduced pressure
to about 5 mL. A yellow solid separated out, which was isolated
by filtration and crystallized from CH2Cl2 and ethanol; yield g80%.
Complex 1a can be also prepared by starting from MnBr(CO)3-
[PPh(OEt)2]2 and using the same reaction conditions; yield g80%.
IR (KBr; cm-1): νCO 2051 (m), 1976, 1906 (s). 1H NMR (CD2Cl2,
25 °C; δ): 7.70-7.30 (m, 10 H, Ph), 4.19, 3.95 (m, 8 H, CH2),
1.34 (t, 12 H, CH3). 119Sn NMR (CD2Cl2, -70 °C; δ): A2M spin
system (A ) 31P, M ) 119Sn), δM 142.6, JAM ) 459.0. 31P{1H}
NMR (CD2Cl2, 25 °C; δ): 185.6 (s, br). 31P{1H} NMR (CD2Cl2,
-70 °C; δ): A2, δA 189.6 (JA117Sn ) 441.5 Hz). Anal. Calcd for
C23H30Cl3MnO7P2Sn: C, 36.33; H, 3.98; Cl, 13.99. Found: C,
36.18; H, 4.07; Cl, 14.11.
Re(SnCl3)(CO)nP5-n (2, 3: P ) PPh(OEt)2 (a), P(OEt)3 (b);
n ) 3 (2), 2 (3)). Method A. In a 100 mL three-necked round-
bottomed flask were placed solid samples of the appropriate
ReCl(CO)nP5-n complex (1.5 mmol), an excess of SnCl2‚2H2O (6
mmol, 1.35 g), and 40 mL of ethanol. The reaction mixture was
refluxed for 5 h, and the solution was then evaporated under reduced
pressure to about 5 mL. The white solid that separated out was
isolated by filtration and crystallized from CH2Cl2 and ethanol; yield
for 2 g70%, yield for 3 g90%.
C, 30.98; H, 3.39; Cl, 11.93. Found: C, 31.15; H, 3.27; Cl, 11.73.
3a. IR (KBr; cm-1): νCO 1986, 1929 (s). 1H NMR (CD2Cl2, 25
°C; δ): 7.85-7.40 (m, 15 H, Ph), 3.94, 3.80, 3.68 (m, 12 H, CH2),
1.37, 1.31, 1.28 (t, 18 H, CH3). 119Sn NMR (CD2Cl2, 25 °C; δ):
AB2M (A, B ) 31P, M ) 119Sn), δM -107.9, JAM ) 324.0, JBM
)
299.4 Hz. 31P{1H} NMR (CD2Cl2, 25 °C; δ): AB2, δA 136.9, δB
136.9, JAB ) 35.1 (JA Sn ) 314.2, JB Sn ) 290.5). 13C{1H} NMR
(CD2Cl2, 25 °C; δ): 193.1 (JCP ) 55, JCP ) 10), 192.5 (JCP ) JCP
) 10) (dt, CO), 140-128 (m, Ph), 65.1, 64.4 (t), 63.5 (d) (CH2),
16.2 (m), 16.1 (d) (CH3). Anal. Calcd for C32H45Cl3O8P3ReSn: C,
36.20; H, 4.27; Cl, 10.02. Found: C, 36.04; H, 4.38; Cl, 9.85.
117
117
3b. IR (KBr; cm-1): νCO 1988, 1937 (s). 1H NMR (CD2Cl2, 25
°C; δ): 4.07 (m, 18 H, CH2), 1.34, 1.32 (t, 27 H, CH3). 119Sn NMR
(CD2Cl2, 25 °C; δ): AB2M, δM -160.6, JAM ) 382.9, JBM ) 324.6
Hz. 31P{1H} NMR (CD2Cl2, 25 °C; δ): AB2, δA 116.2, δB 115.0,
117
117
JAB ) 46.0 (JA Sn ) 361.7, JB Sn ) 311.2). Anal. Calcd for C20H45-
Cl3O11P3ReSn: C, 24.87; H, 4.70; Cl, 11.01. Found: C, 24.72; H,
4.10; Cl, 11.25.
M(SnH3)(CO)nP5-n (4-6) (M ) Mn (4), Re (5, 6); P ) PPh-
(OEt)2 (a), P(OEt)3 (b); n ) 3 (4, 5), 2 (6)). An excess of NaBH4
(19 mmol, 0.72 g) in ethanol (10 mL) was added to a suspension
of the appropriate trichlorostannyl complex M(SnCl3)(CO)nP5-n
(0.95 mmol) in ethanol (40 mL), and the reaction mixture was
refluxed for 15 min for manganese complexes and 45 min for
rhenium complexes. The solvent was removed under reduced
pressure to give a solid, from which the [M]-SnH3 complex was
extracted with three 30 mL portions of benzene. The extracts were
evaporated to dryness, leaving an oil which was triturated with
ethanol (3 mL). A yellow (Mn) or white (Re) solid slowly separated
out from the resulting solution, which was isolated by filtration
and crystallized from ethanol; yield g60% (4), g75% (5, 6).
4a. IR (KBr; cm-1): νCO 2000 (m), 1930, 1914 (s); νSnH 1798,
3
1
1750 (m). H NMR ((CD3)2CO, 25 °C; δ): 7.68-7.44 (m, 10 H,
1
Ph), 4.04, 3.86 (m, 8 H, CH2), A2X3 spin system (X ) H), δX
117
3.40, JAX ) 2.25 Hz (JX Sn ) 1358.5) (3 H, SnH3), 1.32 (t, 12 H,
1
CH3). 119Sn NMR ((CD3)2CO, 25 °C; δ): A2MX3 (X ) H), δM
-259.7, JAM ) 229.7, JAX ) 2.25, JXM ) 1419.2. 31P{1H} NMR
117
((CD3)2CO, -70 °C; δ): A2, δA 200.8 (JA Sn ) 220). Anal. Calcd
for C23H33MnO7P2Sn: C, 42.04; H, 5.06. Found: C, 42.16; H, 5.12.
5a. IR (KBr; cm-1): νCO 2043 (m), 1940, 1922 (s); νSnH 1786,
3
1
1742 (m). H NMR ((CD3)2CO, 25 °C; δ): 7.70-7.35 (m, 10 H,
117Sn
Ph), 3.98, 3.82 (m, 8 H, CH2), A2X3, δX 2.82, JAX ) 3.2 Hz, (JX
) 1255) (3 H, SnH3), 1.32 (t, 12 H, CH3). 119Sn NMR ((CD3)2CO,
25 °C; δ): A2MX3, δM -468.4, JAM ) 151.0, JAX ) 3.2, JXM
)
1321. 31P{1H} NMR ((CD3)2CO, 25 °C; δ): A2, δA 134.1 (JA
117Sn
) 143.8). 13C{1H} NMR ((CD3)2CO, 25 °C; δ): 197.1 (JCP ) 11.3),
192.0 (JCP ) 9.0) (t, CO), 141-128 (m, Ph), 63.2 (t, CH2), 16.0 (t,
CH3). Anal. Calcd for C23H33O7P2ReSn: C, 35.04; H, 4.22.
Found: C, 34.88; H, 4.11.
6a: IR (KBr; cm-1): νCO 1971, 1904 (s); νSnH 1752, 1739 (m).
3
1H NMR ((CD3)2CO, 25 °C; δ): 7.85-7.34 (m, 15 H, Ph), 3.88,
3.73, 3.62 (m, 12 H, CH2), AB2X3, δX 2.70, JAX ) 3.8, JBX ) 3.7
117
Hz (JX
) 1135) (3 H, SnH3), 1.26, 1.25, 1.24 (t, 18 H, CH3).
Method B. In a 50 mL three-necked round-bottomed flask were
placed 0.67 g (1 mmol) of ReH(CO)3[PPh(OEt)2]2, an excess of
anhydrous SnCl2 (4 mmol, 0.76 g), and 30 mL of toluene. The
reaction mixture was stirred at room temperature for 20 h and the
solvent then evaporated to dryness under reduced pressure. The
resulting solid was extracted with three 20 mL portions of CH2-
Cl2, and the extracts were evaporated to dryness. The oil was
triturated with ethanol until a white solid separated out, which was
isolated by filtration and crystallized from CH2Cl2 and ethanol; yield
g75% (2a).
Sn
119Sn NMR ((CD3)2CO, 25 °C; δ): AB2MX3, δM -454.8, JAM
)
228.1, JAX ) 3.8, JBM ) 200.3, JBX ) 3.7, JXM ) 1188. 31P{1H}
NMR ((CD3)2CO, 25 °C; δ): AB2, δA 138.6, δB 134.3, JAB ) 36.0
) 191.4). 13C{1H} NMR ((CD3)2CO, 25
117Sn
(JA
117Sn
) 221.3, JB
°C; δ): 196.2, 194.6 (m, CO), 143-127 (m, Ph), 63.5 (m), 62.3
(d) (CH2), 16.2 (m, CH3). Anal. Calcd for C32H48O8P3ReSn: C,
40.10; H, 5.05. Found: C, 40.03; H, 5.11.
6b. IR (KBr; cm-1): νCO 1971, 1895 (s); νSnH 1752, 1735 (m).
3
1H NMR ((CD3)2CO, -70 °C; δ): 4.01 (m, 18 H, CH2), AB2X,
2a. IR (KBr; cm-1): νCO 2066 (m), 1995 (sh), 1976 (s). 1H NMR
(CD2Cl2, 25 °C; δ): 7.70-7.45 (m, 10 H, Ph), 3.98 (m, 8 H, CH2),
1.40 (t, 12 H, CH3). 119Sn NMR (CD2Cl2, -70 °C; δ): A2M, δM
δX 2.82, JAX ) JBX ) 3.8 Hz (JX Sn ) 1121.7) (3 H, SnH3), 1.27,
117
1.26 (t, 27 H, CH3). 119Sn NMR ((CD3)2CO, 25 °C; δ): AB2MX3,
δM -487.5, JAM ) 254.7, JAX ) 3.8, JBM ) 225.5, JBX ) 3.8, JXM

Stannyl Complexes of Mn and Re
Organometallics, Vol. 26, No. 11, 2007 2921
) 1182.4. 31P{1H} NMR ((CD3)2CO, -70 °C; δ): AB2, δA 122.9,
°C; δ): AB2M, δM -110.6, JAM ) 240.8, JBM ) 210.8. 31P{1H}
NMR (CD2Cl2, 25 °C; δ): AB2, δA 124.1, δB 122.3, JAB ) 47.7
117
117
δB 122.4, JAB ) 45.6 (JA Sn ) 241.6, JB Sn ) 216.4). Anal. Calcd
) 197.2). 13C{1H} NMR (CD2Cl2, 25 °C;
117
117
for C20H48O11P3ReSn: C, 27.85; H, 5.61. Found: C, 27.68; H, 5.64.
(JA
) 228.8, JB
Sn
Sn
δ): 200.4 (JCP ) 70.0, JCP ) 11.5), 196.9 (JCP ) JCP ) 11.0) (dt,
Re(SnD3)(CO)3[PPh(OEt)2]2 (5a1). This compound was pre-
pared exactly like the related unlabeled 5a, using NaBD4 in C2H5-
CO), 61.4 (m), 61.3 (d) (CH2), 16.4 (m, CH3 phos), -3.77 (s,
117
13C119
OD as a reagent. IR (KBr; cm-1): νSnD 1265, 1246 (m).
SnCH3, J
Sn ) 159, J13C Sn ) 153). Anal. Calcd for C23H54O11P3-
3
ReSn: C, 30.54; H, 6.02. Found: C, 30.37; H, 6.10.
M(SnMe3)(CO)3[PPh(OEt)2]2 (7a, 8a: M ) Mn (7), Re (8)).
An excess of MgBrMe (1.5 mmol, 0.5 mL of a 3 M solution in
diethyl ether) was added to a suspension of the appropriate
trichlorostannyl complex M(SnCl3)(CO)3P2 (0.25 mmol) in 20 mL
of diethyl ether cooled to -196 °C. The reaction mixture was
brought to room temperature and stirred for 2 h and the solvent
then removed under reduced pressure. Ethanol (10 mL) was added
to the solid obtained, and the resulting suspension was stirred for
1 h. The solvent was removed under reduced pressure to give a
solid, from which the complex was extracted first with two 10 mL
portions of diethyl ether and then with two 10 mL portions of
benzene. The extracts were evaporated to dryness, leaving an oil,
which was triturated with ethanol (3 mL). A pale yellow (Mn) or
white (Re) solid slowly separated out from the resulting solution,
which was isolated by filtration and crystallized from ethanol; yield
g55%.
Mn[Sn(CtCH)3](CO)3[PPh(OEt)2]2 (10a) and Re[Sn(Ct
CH)3](CO)2[PPh(OEt)2]3 (11a). An excess of MgBr(CtCH) (2.0
mmol, 0.8 mL of a 2.5 M solution in diethyl ether) was added to
a suspension of the appropriate trichlorostannyl complex M(SnCl3)-
(CO)nP5-n (0.33 mmol) in 20 mL of diethyl ether cooled to -196
°C. The reaction mixture was warmed to room temperature and
stirred for 20 h. The solvent was removed under reduced pressure
to give a solid, which was treated with ethanol (5 mL). The resulting
suspension was vigorously stirred at 0 °C until a solid began to
separate out. After the precipitation was completed (about 2-3 h),
the solid was isolated by filtration and crystallized from benzene
and ethanol; yield g40%.
10a. IR (KBr; cm-1): νCH 3275 (m); νCO 2018 (m), 1955, 1930
1
(s). H NMR ((CD3)2CO, -70 °C; δ): 7.83, 7.48 (m, 10 H, Ph),
1
119
4.09, 3.94 (m, 8 H, CH2), 2.53 (s, 3 H, tCH, J H
) 13.8 Hz),
Sn
1.38 (t, 12 H, CH3). 119Sn NMR ((CD3)2CO, -70 °C; δ): A2M,
1
7a. IR (KBr; cm-1): νCO 1979 (m), 1915, 1890 (s). H NMR
δM -174.2, JAM ) 330.1. 31P{1H} NMR ((CD3)2CO, -70 °C; δ):
(CD2Cl2, 25 °C; δ): 7.72-7.38 (m, 10 H, Ph), 4.02, 3.84 (m, 8 H,
A2, δA 194.7 (JA
) 324.5). 13C{1H} NMR ((CD3)2CO, 25 °C;
117
1
119
CH2), 1.31 (t, 12 H, CH3 phos), 0.22 (s, 9 H, SnCH3, J H Sn ) 42
Sn
Hz). 119Sn{1H} NMR (CD2Cl2, -70 °C; δ): A2M, δM 56.5, JAM
179.4. 31P{1H} NMR (CD2Cl2, -70 °C; δ): A2, δA 202.2 (JA
)
δ): 219.0 (JCP ) 15), 217.3 (JCP ) 15) (t, CO), 132-129 (m, Ph),
95.2 (s, Câ, J ) 61), 94.1 (s, CR, J ) 303, J
13C119Sn
13C119Sn
13C117Sn
117Sn
)
) 170.5). 13C{1H} NMR (CD2Cl2, -70 °C; δ): 219.3 (JCP ) 15),
285), 64.0 (t, CH2), 16.1 (t, CH3). Anal. Calcd for C29H33MnO7P2-
Sn: C, 47.77; H, 4.56. Found: C, 47.65; H, 4.44.
218.0 (JCP ) 15) (t, CO), 141-128 (m, Ph), 62.8 (t, CH2), 16.5 (t,
1
11a. IR (KBr; cm-1): νCH 3269 (m); νCO 1976, 1902 (s). H
13C119
13C117
CH3 phos), -3.13 (s, SnCH3, J
Sn ) 209, J
Sn ) 203). Anal.
Calcd for C26H39MnO7P2Sn: C, 44.67; H, 5.62. Found: C, 44.85;
H, 5.69.
NMR ((CD3)2CO, 25 °C; δ): 7.98-7.36 (m, 15 H, Ph), 4.05-
1
119
3.60 (m, 12 H, CH2), 2.20 (s, 3 H, tCH, J H Sn ) 19.6 Hz), 1.33,
1.27, 1.25 (t, 18 H, CH3). 119Sn NMR ((CD3)2CO, -70 °C; δ):
AB2M, δM -361.3, JAM ) 283.0, JBM ) 253.1. 31P{1H} NMR
1
8a. IR (KBr; cm-1): νCO 2013 (m), 1940, 1920 (s). H NMR
((CD3)2CO, 25 °C; δ): 7.62-7.44 (m, 10 H, Ph), 3.95, 3.78 (m, 8
117Sn
((CD3)2CO, 25 °C; δ): AB2, δA 135.2, δB 131.4, JAB ) 36.6 (JA
H, CH2), 1.32, 1.30 (t, 12 H, CH3 phos), 0.19 (s, 9 H, SnCH3,
) 245.1). 13C{1H} NMR ((CD3)2CO, 25 °C; δ):
) 36 Hz). 119Sn{1H} NMR ((CD3)2CO, 25 °C; δ): A2M,
117Sn
) 271.7, JB
1
119Sn
J H
δM -100.7, JAM ) 122.8. 31P{1H} NMR ((CD3)2CO, 25 °C; δ):
A2, δA 135.7 (JA
195.8 (m), 194.5 (dt) (JCP ) JCP ) 10.0) (CO), 142-128 (m, Ph),
97.2 (s, CR, J ) 187), 93.2 (s, Câ, J ) 37.6), 64.3,
) 118.2). 13C{1H} NMR ((CD3)2CO, 25 °C;
13C119Sn
13C119Sn
117
Sn
63.7 (t), 62.8 (d) (CH2), 16.0 (m, CH3). Anal. Calcd for C38H48O8P3-
ReSn: C, 44.29; H, 4.69. Found: C, 44.08; H, 4.81.
δ): 200.0 (JCP ) 11.5), 193.7 (JCP ) 10 Hz) (t, CO), 141-128
(m, Ph), 62.6 (m), 62.3 (d) (CH2), 15.9 (m, CH3 phos), -5.7 (s,
13C119Sn
13C117Sn
SnCH3, J
) 194.7, J
) 186.7). Anal. Calcd for
M[Sn(CtC-p-tolyl)3](CO)n[PPh(OEt)2]5-n (12a-14a: M )
Mn (12), Re (13, 14); n ) 3 (12, 13), 2 (14)). An excess of the
lithium acetylide Li[CtC-p-tolyl] (1.2 mmol, 0.8 mL of a 1.5 M
solution in tetrahydrofuran (thf)) was added to a suspension of the
appropriate trichlorostannyl complex M(SnCl3)(CO)nP5-n (0.3
mmol) in 20 mL of diethyl ether cooled to -196 °C. The reaction
mixture was warmed to room temperature and stirred for 3 h, and
the solvent was then removed under reduced pressure. The oil
obtained was treated with ethanol (5 mL), and the resulting solution
was stirred at 0 °C until a solid separated out. In the case of
manganese, the solid separated out after cooling the solution to
-25 °C. The solids were isolated by filtration and crystallized from
benzene and ethanol; yields ranged from 75% (Re) to 50% (Mn).
C26H39O7P2ReSn: C, 37.61; H, 4.73. Found: C, 37.74; H, 4.63.
Re(SnMe3)(CO)2P3 (9: P ) PPh(OEt)2 (a), P(OEt)3 (b)). An
excess of MgBrMe (1.5 mmol, 0.5 mL of a 3 M solution in diethyl
ether) was added to a solution of the appropriate trichlorostannyl
complex Re(SnCl3)(CO)2P3 (0.25 mmol) in 30 mL of diethyl ether
cooled to -196 °C. The reaction mixture was warmed to room
temperature and stirred for 3 h and the solvent then removed under
reduced pressure. The solid obtained was treated with ethanol (5
mL) and the resulting solution stirred for 1 h. A white solid slowly
separated out by allowing the solution to stand at -25 °C for some
days. The solid was isolated by filtration and crystallized from CH2-
Cl2 and ethanol; yield g60%.
12a. IR (KBr; cm-1): νCtC 2132 (m); νCO 2007 (w), 1938, 1927
(s). 1H NMR (CD2Cl2, 25 °C; δ): 7.85-7.13 (m, 22 H, Ph), 4.08,
3.94 (m, 8 H, CH2), 2.35 (s, 9 H, CH3 p-tolyl), 1.36 (t, 12 H, CH3
9a. IR (KBr; cm-1): νCO 1962, 1880 (s). 1H NMR (CD2Cl2, 25
°C; δ): 7.70-7.33 (m, 15 H, Ph), 4.00-3.50 (m, 12 H, CH2), 1.27,
1
119Sn
1.25, 1.23 (t, 18 H, CH3 phos), -0.10 (s, 9 H, SnCH3, J H
)
phos). 119Sn NMR (CD2Cl2, -70 °C; δ): A2M, δM -166.3, JAM
353.5 Hz. 31P{1H} NMR (CD2Cl2, -70 °C; δ): A2, δA 195.8 (JA
)
32 Hz). 119Sn NMR (CD2Cl2, 25 °C; δ): AB2MX9, δM -126.7,
JAM ) 210.8, JAX ) 0.1, JBM ) 185.3, JBX ) 0.1, JXM ) 32. 31P-
117Sn
) 338.4). 13C{1H} NMR (CD2Cl2, 25 °C; δ): 219 (m, CO), 138-
{1H} NMR (CD2Cl2, -70 °C; δ): AB2, δA 140.9, δB 136.1, JAB
)
37.0 (JA Sn ) 192.7, JB Sn ) 178.0). 13C{1H} NMR (CD2Cl2, 25
°C; δ): 200.4 (JCP ) 58, JCP ) 10), 196.7 (JCP ) JCP ) 9.8) (dt,
CO), 142-128 (m, Ph), 63.1, 62.9 (t), 61.9 (d) (CH2), 16.5 (m),
117
13C119Sn
Sn
117
117
121 (m, Ph), 107.3 (s, Câ, J
) 66, J13C
) 63), 98.2 (s,
13C119Sn
13C117Sn
CR, J
) 312, J
) 297), 65.5 (t, CH2), 21.6 (s, CH3
p-tolyl), 16.2 (t, CH3 phos). Anal. Calcd for C50H51MnO7P2Sn: C,
13C119
60.08; H, 5.14. Found: C, 60.26; H, 5.25.
16.3 (d) (CH3 phos), -3.21 (s, SnCH3, J
Sn ) 145). Anal. Calcd
13a. IR (KBr; cm-1): νCtC 2131 (m); νCO 2036 (m), 1951, 1937
(s). 1H NMR (CD2Cl2, 25 °C; δ): 7.80-7.12 (m, 22 H, Ph), 4.04,
3.99 (m, 8 H, CH2), 2.36 (s, 9 H, CH3 p-tolyl), 1.37 (t, 12 H, CH3
for C35H54O8P3ReSn: C, 42.01; H, 5.44. Found: C, 41.83; H, 5.37.
9b. IR (KBr; cm-1): νCO 1951, 1882 (s). 1H NMR (CD2Cl2, 25
°C; δ): 4.10 (m, 18 H, CH2), 1.31, 1.28 (t, 27 H, CH3 phos), 0.06
(s, 9 H, SnCH3, J H
) 36 Hz). 119Sn{1H} NMR (CD2Cl2, 25
phos). 119Sn NMR (CD2Cl2, 25 °C; δ): A2M, δM -342.3, JAM
)
1
119Sn

2922 Organometallics, Vol. 26, No. 11, 2007
Table 1. Crystal Data and Structure Refinement Details
Albertin et al.
Mn(SnH3)(CO)3-
[PPh(OEt)2]2 (4a)
Re(SnH3)(CO)2-
[P(OEt)3]3 (6b)
Re(SnMe3)(CO)2-
[P(OEt)3]3 (9b)
[Re{Sn[OC(H)dO]2}(µ-OH)(CO)2-
{P(OEt)3}3]2 (16b)
empirical formula
formula wt
C23H33MnO7P2Sn
657.06
C20H48O11P3ReSn
862.38
C46H108O22P6Re2Sn2
1808.92
C44H96O32P6Re2Sn2
1932.85
temp, K
173(2)
173(2)
293(2)
293(2)
wavelength, Å
0.710 73
0.71073
0.71073
0.71073
cryst syst, space group
unit cell dimens
monoclinic, P21/c
monoclinic, P21/n
monoclinic, P21/c
triclinic, P1h
a, Å
b, Å
c, Å
19.724(3)
9.3980(12)
17.039(2)
90
115.347(2)
90
17.267(3)
11.6003(18)
18.095(3)
90
112.887(3)
90
28.120(2)
10.7089(9)
30.4873(17)
90
122.795(5)
90
11.1114(11)
11.9510(13)
16.5529(17)
109.711(2)
92.817(2)
114.348(2)
1839.3(3)
2
R, deg
â, deg
γ, deg
V, Å3
2854.3(6)
4
3339.1(9)
4
7717.5(10)
4
Z
calcd density, Mg/m3
abs coeff, mm-1
data completeness
goodness of fit on F2
final R indices (I > 2θ(I))
R1
1.529
1.466
0.944
0.925
1.715
4.559
0.952
0.850
1.557
3.949
0.894
0.750
1.745
4.158
0.890
0.897
0.0533
0.1157
0.0336
0.0557
0.0560
0.0862
0.0459
0.0900
wR2
R indices (all data)
R1
0.1020
0.0577
0.2602
0.0684
wR2
0.1282
1.354, -0.641
0.0597
1.546, -1.457
0.1198
2.378, -0.602
0.0965
1.700, -1.609
largest diff peak, hole, e Å-3
197.0 Hz. 31P{1H} NMR (CD2Cl2, 25 °C; δ): A2, δA 131.9 (JA
δ): 9.21 (s, 4 H, CHO), 8.91 (s, 2 H, µ-OH), 4.12 (m, 36 H, CH2),
1.37 (m, 54 H, CH3). 119Sn NMR (CD3C6D5, 25 °C; δ): AB2M,
δM -487.7, JAM ) 367.0, JBM ) 328.5 Hz. 31P{1H} NMR
117Sn
) 188.6). 13C{1H} NMR (CD2Cl2, 25 °C; δ): 193.4 (JCP ) 10.9),
13C119Sn
189.8 (JCP ) 9.0) (t, CO), 140-122 (m, Ph), 107.2 (s, Câ, J
117
13C119
13C117
117Sn
) 69, J13C Sn ) 67), 97.3 (s, CR, J
Sn ) 295, J
Sn ) 289),
(CD3C6D5, -70 °C; δ): A2B, δA 117.9, δB 116.1, JAB ) 48.6 (JA
) 311.4). 13C{1H} NMR (CD3C6D5, 25 °C; δ):
117Sn
) 338.6, JB
63.7 (t, CH2), 21.5 (s, CH3 p-tolyl), 16.1 (t, CH3 phos). Anal. Calcd
for C50H51O7P2ReSn: C, 53.11; H, 4.55. Found: C, 52.92; H, 4.46.
14a. IR (KBr; cm-1): νCtC 2131 (m); νCO 1975, 1902 (s). H
198.0, 195.5 (m, CO), 166.4 (s, CHO), 62.8 (t, CH2), 16.2 (t, CH3).
Anal. Calcd for C44H96O32P6Re2Sn2: C, 27.34; H, 5.01. Found: C,
27.15; H, 5.13.
Crystal Structure Determination. Data were collected on a
SIEMENS Smart CCD area-detector diffractometer with graphite-
monochromated Mo KR radiation. Absorption correction was
carried out by SADABS.11
Crystallographic calculations were performed with the Oscail
program.12 Structures were solved by direct methods and refined
by a full-matrix least-squares method based on F2.13 Non-hydrogen
atoms were refined with anisotropic displacement parameters.
Hydrogen atoms were included in idealized positions and refined
with isotropic displacement parameters, except those bonded to the
tin atom for 4a and 6b, which were located and refined with
anisotropic displacement parameters, and the hydrogen on the
bridging hydroxyl oxygen atom for complex 15b, which was located
but its position was not refined.
1
NMR (CD2Cl2, 25 °C; δ): 8.00-7.09 (m, 27 H, Ph), 4.00, 3.84,
3.62 (m, 12 H, CH2), 2.35 (s, 9 H, CH3 p-tolyl), 1.33, 1.21, 1.19 (t,
18 H, CH3 phos). 119Sn NMR (CD2Cl2, 25 °C; δ): AB2M, δM
-358.5, JAM ) 280.2, JBM ) 258.5 Hz. 31P{1H} NMR (CD2Cl2,
117
25 °C; δ): AB2, δA 136.9, δB 132.3, JAB ) 35.0 (JA
) 268.0,
Sn
JB Sn ) 246.6). 13C{1H} NMR (CD2Cl2, 25 °C; δ): 196.0 (JCP
)
117
57, JCP ) 9.8), 194.4 (JCP ) JCP ) 9.8) (dt, CO), 141-123 (m,
Ph), 105.8 (s, Câ, J ) 42), 101.4 (s, CR, J ) 195.6,
13C119Sn
13C119Sn
13C117
J
Sn ) 185.8), 63.9, 63.3 (t), 62.2 (d) (CH2), 21.5 (s, CH3 p-tolyl),
16.2 (m, CH3 phos). Anal. Calcd for C59H66O8P3ReSn: C, 54.47;
H, 5.11. Found: C, 54.30; H, 5.03.
[Re{Sn[OC(H)dO]2(µ-OH)}(CO)2P3]2 (15: P ) PPh(OEt)2
(a), P(OEt)3 (b)). A solution of the appropriate trihydride stannyl
complex Re(SnH3)(CO)2P3 (0.1 mmol) in benzene (5 mL) was
allowed to stand under a CO2 atmosphere (1 atm) at room
temperature for 24 h. The solvent was removed under reduced
pressure, to give an oil which was triturated with pentane (5 mL)
and ethanol (1 mL). A white solid slowly separated out, which was
isolated by filtration and crystallized from acetone and ethanol; yield
g80%.
Atomic scattering factors and anomalous dispersion corrections
for all atoms were taken from ref 14. Details of crystal data and
structural refinements are given in Table 1.
Results and Discussion
15a. IR (KBr; cm-1): νCO 1989, 1926 (s); νCHO 1674 (m), 1636
The chloro complexes15 MCl(CO)nP5-n (M ) Mn, Re; P )
PPh(OEt)2, P(OEt)3; n ) 2, 3) react with an excess of SnCl2‚
1
(s). H NMR ((CD3)2CO, 25 °C; δ): 8.82 (s, 4 H, CHO), 7.90-
6.97 (m, 30 H, Ph), 3.90-3.60 (m, 24 H, CH2), 1.22, 1.17, 1.13 (t,
36 H, CH3). 1H NMR ((CD3)2CO, -70 °C; δ): 9.72 (s, 4 H, CHO),
8.90 (s, 2 H, µ-OH),7.95-6.90 (m, 30 H, Ph), 4.20-3.40 (m, 24
H, CH2), 1.43 (t, 36 H, CH3). 119Sn NMR ((CD3)2CO, 25 °C; δ):
AB2M, δM -496.6, JAM ) 353.8, JBM ) 341.0 Hz. 31P{1H} NMR
((CD3)2CO, -30 °C; δ): AB2, δA 133.9, δB 133.0, JAB ) 39.8
(11) Sheldrick, G. M. SADABS: An Empirical Absorption Correction
Program for Area Detector Data; University of Go¨ttingen, Go¨ttingen,
Germany, 1996.
(12) McArdle, P. J. Appl. Crystallogr. 1995, 28, 65.
(13) Sheldrick, G. M. SHELX-97: Program for the Solution and
Refinement of Crystal Structures; University of Go¨ttingen, Go¨ttingen,
Germany, 1997.
(14) International Tables for X-ray Crystallography; Kluwer: Dordrecht,
The Netherlands, 1992; Vol. C.
(15) The halogeno complexes MX(CO)nP5-n (X ) Cl, Br; P ) PPh-
(OEt)2, P(OEt)3; n ) 2, 3) were prepared by substituting carbonyl ligands
with phosphites in pentacarbonyl precursors MX(CO)5, following the method
reported in the Experimental Section. Analytical and spectroscopic data
support the proposed formulation.
) 325.1). 13C{1H} NMR ((CD3)2CO, 25
117Sn
(JA
117Sn
) 335.2, JB
°C; δ): 193.2, 192.2 (m, CO), 166.0 (s, CHO), 140-124 (m, Ph),
64.1, 63.2 (m, CH2), 16.0 (m, CH3). Anal. Calcd for C68H96O26P6-
Re2Sn2: C, 38.43; H, 4.55. Found: C, 38.26; H, 4.62.
15b: IR (KBr; cm-1): νCO 1988, 1919 (s); νCHO 1665 (m), 1594
1
(s). H NMR (CD3C6D5, 25 °C; δ): 8.85 (s, 4 H, CHO), 4.02 (m,
1
36 H, CH2), 1.23 (m, 54 H, CH3). H NMR (CD3C6D5, -70 °C;

Stannyl Complexes of Mn and Re
Scheme 1
Organometallics, Vol. 26, No. 11, 2007 2923
a
tion is supported by analytical and spectroscopic data (IR and
1H, 31P, and 119Sn NMR) and by the X-ray crystal structure
determinations of the derivatives Mn(SnH3)(CO)3[PPh(OEt)2]2
(4a) and Re(SnH3)(CO)2[P(OEt)3]3 (6b).
The IR spectra of the [M]-SnCl3 tricarbonyl complexes (1,
2) in the νCO region show one band of medium intensity and
two strong bands between 2066 and 1906 cm-1, suggesting a
mer arrangement of the three carbonyl ligands.17 In the
temperature range between +20 and -80 °C, the 31P NMR
spectra appear as sharp singlets, fitting the magnetic equivalence
of the two phosphite ligands. The spectra also show the
characteristic satellites due to the coupling with the 119Sn and
117Sn nuclei of the SnCl3 ligand. However, the presence of the
stannyl ligand is confirmed by 119Sn NMR spectra, in which it
appears as triplets, due to coupling with the two magnetically
equivalent phosphorus nuclei. On the basis of these data, a mer-
trans geometry of type I (Scheme 1) may be proposed for
trichlorostannyl derivatives 1 and 2.
a Legend: M ) Mn (1, 4), Re (2, 5); P ) PPh(OEt)2 (a).
a
Scheme 2
The IR spectra of the related dicarbonyl complexes Re-
(SnCl3)(CO)2P3 (3) show two νCO bands at 1988-1929 cm-1
,
in agreement with the mutually cis position of the two carbonyl
ligands. The 13C NMR spectra of 3a also indicate the magnetic
inequivalence of the two CO groups, showing two well-
separated multiplets for carbonyl carbon resonances. As 31P
spectra appear as AB2 multiplets, with 119Sn and 117Sn satellites,
a mer-cis geometry of type II (Scheme 2) may reasonably be
proposed for trichlorostannyl derivatives 3.
a Legend: P ) PPh(OEt)2 (a), P(OEt)3 (b).
The IR spectra of the trihydridostannyl complexes M(SnH3)-
(CO)3[PPh(OEt)2]2 (4, 5), in addition to the three νCO bands
characteristic of a mer arrangement, show two medium-intensity
bands at 1798-1742 cm-1, attributed to the νSnH band of the
SnH3 ligand. In the labeled complex Re(SnD3)(CO)3[PPh-
(OEt)2]2 (5a1), the two νSnD bands were observed at 1265 and
1246 cm-1, thus confirming the proposed attribution. Diagnostic
2H2O in refluxing ethanol to give the trichlorostannyl derivatives
M(SnCl3)(CO)nP5-n (1-3) in high yields. Treatment of these
[M]-SnCl3 compounds with NaBH4 in ethanol affords the
trihydridostannyl complexes M(SnH3)(CO)nP5-n (4-6), which
were separated as pale yellow or white microcrystals and
characterized (Schemes 1 and 2).
1
The insertion of SnCl2 into the M-Cl bond, to give
trichlorostannyl complexes 1-3, is slow at room temperature
and needs reflux conditions for good yields. It may be noted
that the SnCl3 ligand in 1-3 also forms by starting from the
bromide precursors MBr(CO)nP5-n, probably through the initial
metathetic reaction with SnCl2, giving the chloro intermediate
MCl(CO)nP5-n. Halide exchange between the first-formed mixed
trihalostannyl complex [M]-SnBrCl2 and SnCl2 in excess
cannot be excluded. Surprisingly, the trichlorostannyl complexes
[M]-SnCl3 1-3 can also be obtained from the reaction of the
hydrides MH(CO)nP5-n with anhydrous SnCl2. A first reaction
of the hydride with SnCl2, to give the chloro complex
MCl(CO)nP5-n followed by the insertion of SnCl2 into the M-Cl
bond, may explain the formation of the [M]-SnCl3 complex.
However, the direct insertion of SnCl2 into the metal-hydride
bond to give the hydridodihalostannyl intermediate [M]-SnHCl2
is also plausible. Halide exchange may then give the final
[M]-SnCl3 derivatives 1-3.
The trichlorostannyl complexes [M]-SnCl3 undergo substitu-
tion of all three chlorides with H- when NaBH4 is used as a
reagent, thus allowing the synthesis of the first complexes of
Mn and Re (4-6) containing tin trihydride as a ligand. Crucial
for the success of syntheses was the use of very pure samples
of precursors 1-3 and of an appropriate reaction time.
Otherwise, only large amounts of decomposition products or
very impure materials were isolated.
for the presence of tin trihydride as a ligand are both H and
119Sn NMR spectra. In the proton spectra a triplet, with the
characteristic satellites due to coupling with 119Sn and 117Sn,
was observed at 3.40 ppm for the manganese complex 4a and
at 2.82 ppm for the rhenium complex 5a (Figure S1), which
was attributed to the SnH3 group. Proton- and phosphorus-
coupled 119Sn spectra appear as quartets of doublets at -259.7
ppm (4a) (Figure S2) and -468.4 ppm (5a), due to coupling
with three hydrides and the two magnetically equivalent
phosphorus nuclei, confirming the presence of the SnH3 group.
In the temperature range between +20 and -80 °C, the 31P
NMR spectra of rhenium complex 5a are in fact sharp singlets,
indicating the magnetic equivalence of the two phosphite
ligands. Instead, the spectrum of the related manganese deriva-
tive 4a is broad at room temperature but resolves into a sharp
singlet at -70 °C, suggesting the magnetic equivalence of the
two phosphite ligands in this case as well. On the basis of these
data, a mer-trans geometry of type III (Scheme 1), like that
found in the solid state for 4a (see below), may reasonably be
proposed for the trihydridostannyl derivatives M(SnH3)(CO)3P2
(4, 5).
The IR spectra of the related dicarbonyl complexes Re(SnH3)-
(CO)2P3 (6a, 6b) show two νCO bands at 1971-1895 cm-1 of
two carbonyls in a mutually cis position and two medium-
intensity absorptions at 1752-1735 cm-1, due to the νSnH band
of the SnH3 ligand. The 1H NMR spectra confirm the presence
of the trihydridostannyl group, showing multiplets at 2.70 ppm
(6a) and 2.8 ppm (6b) (at -70 °C), with the characteristic
Stannyl complexes 1-6 were isolated as yellow (Mn) or white
(Re) solids, stable in air and in solutions of common organic
solvents, where they behave as nonelectrolytes.16 Their formula-
(17) Adams, D. M. Metal-ligand and Related Vibrations; St. Martin’s
Press: New York, 1968.
(16) Geary, W. J. Coord. Chem. ReV. 1971, 7, 81-122.

2924 Organometallics, Vol. 26, No. 11, 2007
Albertin et al.
those concerning the mentioned carbonyl groups. The bond
distance between the carbonyl groups and the manganese atom
is affected by the trans influence, and the Mn-C(1) distance
of the carbonyl trans to the trihydridostannyl group is only
slightly shorter than the Mn-C distances involving the two
carbonyl groups trans to each other. These data let us propose
a trans influence for the SnH3 ligand intermediate between those
of the carbonyl group and the P(OMe)3 group.4 Accordingly,
the corresponding C-O distances follow the opposite trend.
These values are similar to those found in previously reported
mer-tricarbonylmanganese complexes.5a The Mn-P distances
are 2.2303(15) and 2.2335(14) Å and are significantly shorter
than those found in other mer,trans-tricarbonylbis(phosphinite)-
manganese complexes.5a,18
The substituents on the phosphorus atoms are situated in a
pseudo-eclipsed fashion, both phenyl groups following the
direction of one of the carbonyl groups, with torsion angles
C(11)-P(1)-P(2)-C(21), O(11)-P(1)-P(2)-O(22), and O(12)-
P(1)-P(2)-O(21) of only -6.8(3), -2.3(2), and -3.4(3)° and
C(11)-P(1)-Mn-C(2) and C(21)-P(2)-Mn-C(2) of -15.3-
(2) and 8.5(3)°, respectively.
Figure 1. ORTEP view of the complex Mn(SnH3)(CO)3[PPh-
(OEt)2]2 (4a) drawn with thermal ellipsoids at the 30% probability
level. The substituents on the phosphorus atoms were removed for
clarity.
Table 2. Selected Bond Lengths (Å) and Angles (deg) for
Mn(SnH3)(CO)3[PPh(OEt)2]2 (4a)
Sn-H(2)
Sn-H(1)
Mn-C(1)
Mn-C(3)
Mn-P(1)
C(2)-O(2)
1.59(6)
1.81(6)
1.783(6)
1.878(5)
2.2335(14)
1.149(5)
Sn-H(3)
Sn-Mn
Mn-C(2)
Mn-P(2)
C(1)-O(1)
C(3)-O(3)
1.74(6)
2.6260(9)
1.814(5)
2.2303(15)
1.154(6)
1.077(6)
The Sn-H bond lengths (in the range 1.59(6)-1.81(6) Å)4
and angles confirm the sp3 character of the tin atom, but these
values may be misleading due to the well-known limitations of
X-ray diffractometry for hydrogen atoms in the proximity of
heavy metals.
The Mn-Sn bond length, 2.6260(9) Å, is shorter than those
found in bis(pentacarbonylmanganese)diphenyltin19 and in other
(triaryltin)pentacarbonylmanganese(I) complexes.6l
H(2)-Sn-H(3)
H(3)-Sn-H(1)
H(3)-Sn-Mn
C(1)-Mn-C(2)
C(1)-Mn-P(2)
C(3)-Mn-P(2)
C(2)-Mn-P(1)
P(2)-Mn-Sn
96(3)
109(3)
116(2)
96.4(2)
89.86(16)
89.75(14)
90.14(15)
91.48(5)
80.77(18)
178.10(6)
163.2(2)
H(2)-Sn-H(1)
H(2)-Sn-Mn
H(1)-Sn-Mn
C(1)-Mn-C(3)
C(2)-Mn-P(2)
C(1)-Mn-P(1)
C(3)-Mn-P(1)
C(2)-Mn-Sn
P(1)-Mn-Sn
C(1)-Mn-Sn
108(3)
115(2)
110.9(19)
100.2(2)
88.44(15)
89.04(16)
91.98(14)
82.61(16)
89.59(4)
178.33(16)
The perspective view of complex Re(SnH3)(CO)2[P(OEt)3]3
(6b) is shown in Figure 2. Selected bond distances and angles
are given in Table 3. In this compound, the rhenium atom is
coordinated by three phosphorus atoms of the phosphite ligands
in mer positions, two carbonyl ligands in cis positions, and a
tin atom from a trihydridostannyl group. The Re-C bond
distances, 1.922(5) and 1.935(5) Å, show small differences, the
shorter one being trans to the trihydridostannyl ligand, confirm-
ing the trend found previously in the Mn(I) complex. The Re-P
bond distances range from 2.3664(11) to 2.3883(12) Å, being
about 0.02 Å shorter those mutually trans than the one trans to
the carbonyl ligand. Except for the Re-C bond length trans to
the trihydridostannyl ligand, all Re-C and Re-P bond lengths
C(3)-Mn-Sn
P(2)-Mn-P(1)
C(2)-Mn-C(3)
satellites due to coupling with 119Sn and 117Sn. Taking into
account that the 31P spectra are AB2 multiplets, the proton
multiplet can be simulated with an AB2X3 model with the
parameters reported in the Experimental Section. In addition,
the proton-coupled 119Sn NMR spectra appear as complicated
multiplets, due to coupling with the hydride and phosphorus
nuclei, which can be simulated with an AB2MX3 model (M )
are shorter than those found in [ReBr(CO)2{P(OEt)3}3],20
a
1
119Sn; X ) H), in agreement with the presence of the SnH3
rhenium(I) complex with a similar environment. The Re-Sn
bond length, 2.7632(6) Å, is similar to those found in (trialky-
ltin)rhenium(I) complexes21 and is shorter than the sum of the
covalent radii of the metals (∼2.95 Å).
ligand.
The 13C NMR spectrum of the complex Re(SnH3)(CO)2[PPh-
(OEt)2]3 (6a) shows two well-separated multiplets at 196.2 and
194.6 ppm, due to the carbonyl carbon resonances of two
magnetically inequivalent carbonyl ligands. On the basis of these
data, a mer-cis geometry of type IV (Scheme 2), like that
observed in the solid state for 6b, may reasonably be proposed
in solution for our trihydridostannyl derivatives 6.
The angles around the rhenium atom fall well into the range
expected for a regular octahedron, the most distorted value being
that of the P-Re-P axis, 171.94(4)°, which is slightly bent
toward the bisector of the Sn-Re-CO angle. The substituents
on the phosphorus atoms, mutually in trans positions, are situated
in a pseudo-eclipsed fashion, with torsion O-P-P-O angles
of only 5.6(2)° (average), but none of the substituents follow
the same direction as any ligand in the equatorial plane, with
The perspective view of the complex Mn(SnH3)(CO)3[PPh-
(OEt)2]2 (4a) is shown in Figure 1. Selected bond distances and
angles are given in Table 2. The manganese ion is coordinated
by three carbonyl ligands in mer positions, two phosphorus
atoms of two phosphinite ligands in trans positions, and a tin
atom from a trihydridostannyl group. The coordination poly-
hedron around the manganese may be defined as an octahedron,
but some distortion is found in the carbonyl-manganese-
carbonyl axis, with a C(2)-Mn-C(3) angle of 163.2(2)°, bent
toward the position occupied by the trihydridostannyl ligand,
perhaps due to the lower steric requirements for this ligand.
The other two axes are almost linear (178.10(6) and 178.33-
(16)°). The cis angles are close to the theoretical 90°, except
(18) Bravo, J.; Castro, J.; Garcia-Fonta´n, S.; Lamas, E. M.; Rodr´ıguez-
Seoane, P. Z. Anorg. Allg. Chem. 2003, 629, 297-302.
(19) Christendat, D.; Wosnick, J. H.; Butler, I. S.; Gilson, D. F. R.;
Lebuis, A.-M.; Morin, F. G. J. Mol. Struct. 2001, 559, 235-243.
(20) Carballo, R.; Losada-Gonza´lez, P.; Va´zquez-Lo´pez, E. M. Z. Anorg.
Allg. Chem. 2003, 629, 249-254.
(21) (a) Lee, S. W.; Yang, K.; Martin, J. A.; Bott, S. G.; Richmond, M.
G. Inorg. Chim. Acta 1995, 232, 57-62. (b) Lo´pez, E. M.; Miguel, D.;
Pe´rez, J.; V. Riera, V.; Bois, C.; Jeannin, Y. Organometallics 1999, 18,
490-494.

Stannyl Complexes of Mn and Re
Organometallics, Vol. 26, No. 11, 2007 2925
Scheme 3
derivatives,2r,t prepared from the oxidative addition of Ar3SnH
species to precursor complexes in a low oxidation state. The
use of mixed-ligand Re(CO)nP5-n fragments, with carbonyl and
phosphite, allows easy synthesis of mononuclear rhenium
stannyl complexes containing SnCl3 and, for the first time, tin
trihydride (SnH3) as a ligand. Manganese stannyl derivatives6
are better known than rhenium ones, and some years ago a very
unstable stannyl complex,6g formulated as Mn(SnH3)(CO)5, was
obtained from the reaction of Na[Mn(CO)5] with SnH3Cl at -45
°C. The absence of 119Sn and 117Sn satellites in the proton signals
attributed to the SnH3 group in the NMR spectra may have made
its formulation uncertain. However, comparison with the
spectroscopic data of our tin trihydride derivative Mn(SnH3)-
(CO)3[PPh(OEt)2] suggests that the complex prepared by
Mackay et al., although so unstable as to appear as a transient
species, probably did contain the SnH3 ligand. In our case, the
use of the mixed-ligand Mn(CO)3P2 fragment instead of Mn-
(CO)5 allowed easy stabilization of the SnH3 group bonded to
manganese, yielding stable and isolable complexes. The use of
Figure 2. ORTEP views of the complex Re(SnH3)(CO)2[P(OEt)3]3
(6b) drawn with thermal ellipsoids at the 30% probability level.
The substituents on the phosphorus atoms were removed for clarity.
22
NaBH4 to synthesize trihydridostannyl complexes may also
be important in providing a easy route to this new class of
complexes containing SnH3 as a ligand.
Table 3. Selected Bond Lengths (Å) and Angles (deg) for
Re(SnH3)(CO)2[P(OEt)3]3 (6b)
The easy synthesis of trihydridostannyl complexes 4-6, by
substituting chloride with H- in the metal-bonded SnCl3 group,
prompted us to extend the substitution reaction on [M]-SnCl3
complexes 1-3 to other nucleophilic reagents: the results are
shown in Schemes 3 and 4.
Sn-H(1)
Sn-H(3)
Re-C(1)
Re-P(1)
Re-P(3)
C(2)-O(2)
1.81(5)
1.63(5)
1.922(5)
2.3664(11)
2.3883(12)
1.156(5)
Sn-H(2)
Re-Sn
Re-C(2)
Re-P(2)
C(1)-O(1)
1.63(6)
2.7632(6)
1.935(5)
2.3693(11)
1.140(5)
The trichlorostannyl complexes M(SnCl3)(CO)nP5-n react
with both Grignard reagents MgBrMe and MgBr(CtCR) to give
the trimethylstannyl derivatives M(SnMe3)(CO)nP5-n (7-9) and
tris(alkynyl)stannyl derivatives M[Sn(CtCR)3](CO)nP5-n (10-
14), respectively, which can be isolated in the solid state and
characterized. The tris(alkynyl)stannyl complexes 12-14 can
also be prepared by treating [M]-SnCl3 precursors with the
lithium acetylide Li+(CtCR)- in thf. The substitution reaction
is quite fast at room temperature and yields the trisubstituted
stannyl group with a moderate excess of the nucleophile.
Good analytical data were obtained for stannyl complexes
7-14, which were isolated as yellow (Mn) or white (Re) solids,
stable in air and in solution in common organic solvents, where
they behave as nonelectrolytes.16 The compounds were char-
acterized by spectroscopy (IR and 1H, 31P, 13C, and 119Sn NMR)
C(1)-Re-C(2)
C(2)-Re-P(1)
C(2)-Re-P(2)
C(1)-Re-P(3)
P(1)-Re-P(3)
C(1)-Re-Sn
P(1)-Re-Sn
89.33(19)
89.78(13)
83.01(13)
88.69(13)
93.42(4)
177.28(12)
88.04(3)
93.73(3)
100(2)
C(1)-Re-P(1)
C(1)-Re-P(2)
P(1)-Re-P(2)
C(2)-Re-P(3)
P(2)-Re-P(3)
C(2)-Re-Sn
P(2)-Re-Sn
H(2)-Sn-H(3)
H(3)-Sn-H(1)
O(1)-C(1)-Re
90.57(12)
92.94(12)
171.94(4)
176.25(13)
93.92(4)
88.33(15)
88.15(3)
91(3)
P(3)-Re-Sn
H(2)-Sn-H(1)
H(1)-Sn-Re
O(2)-C(2)-Re
101(2)
179.7(4)
116.6(17)
176.8(4)
O-P-Re-P(3) or O-P-Re-C(1) torsion angles of about 15°
and O-P-Re-Sn torsion angles of about 45° (see Figure 2,
bottom).
The Sn-H bond lengths are in the range of 1.63(5)-1.81(5)
Å, as found previously for the Mn(I) complex, but these values
may be misleading, due to the well-known restrictions of X-ray
diffractometry for hydrogen atoms in the proximity of heavy
metals.
(22) The use of NaBH4 as a reagent is rare in the chemistry of tin
ligands,23 which generally involves oxidative addition or nucleophilic
substitution reactions to coordinate tin compounds to metal fragments.
(23) Lappert, M. F.; McGeary, M. J.; Parish, R. V. J. Organomet. Chem.
1989, 373, 107-117.
Relatively few examples of rhenium-tin complexes have
been reported to date2r,t,7 and mainly include di- or polynuclear

2926 Organometallics, Vol. 26, No. 11, 2007
Albertin et al.
Scheme 4
Table 4. Selected Bond Lengths (Å) and Angles (deg) for
Re(SnMe3)(CO)2[P(OEt)3]3 (9b)
molecule 1
molecule 2
Re(1)-C(1)
Re(1)-C(2)
1.81(2)
Re(2)-C(7)
Re(2)-C(6)
Re(2)-P(21)
Re(2)-P(22)
Re(2)-P(23)
1.77(3)
1.904(13)
2.293(4)
2.338(4)
2.354(4)
1.915(15)
2.334(4)
2.342(4)
2.348(4)
2.7929(10)
2.183(13)
2.201(12)
2.221(11)
1.148(13)
1.26(2)
Re(1)-P(11)
Re(1)-P(12)
Re(1)-P(13)
Re(1)-Sn(1)
Sn(1)-C(4)
Sn(1)-C(3)
Sn(1)-C(5)
O(2)-C(2)
2.7917(10) Re(2)-Sn(2)
2.183(11)
2.194(13)
2.212(11)
1.158(12)
1.249(19)
Sn(2)-C(10)
Sn(2)-C(8)
Sn(2)-C(9)
O(6)-C(6)
O(7)-C(7)
O(1)-C(1)
C(1)-Re(1)-C(2)
C(1)-Re(1)-P(11)
C(2)-Re(1)-P(11)
C(1)-Re(1)-P(12)
C(2)-Re(1)-P(12)
92.6(6)
177.8(4)
89.6(4)
88.8(4)
94.5(4)
C(7)-Re(2)-C(6)
C(7)-Re(2)-P(21)
C(6)-Re(2)-P(21)
C(7)-Re(2)-P(22)
C(6)-Re(2)-P(22)
92.1(6)
177.7(5)
90.1(4)
88.6(5)
95.4(4)
Figure 3. ORTEP views of one of the molecules of the asymmetric
unit of the compound Re(SnMe3)(CO)2[P(OEt)3]3 (9b) drawn with
thermal ellipsoids at the 30% probability level. The substituents
on the phosphorus atoms were removed for clarity.
P(11)-Re(1)-P(12) 91.03(14)
P(21)-Re(2)-P(22) 92.01(13)
C(1)-Re(1)-P(13)
C(2)-Re(1)-P(13)
P(11)-Re(1)-P(13) 91.29(15)
P(12)-Re(1)-P(13) 170.62(14) P(22)-Re(2)-P(23) 169.54(13)
C(1)-Re(1)-Sn(1)
C(2)-Re(1)-Sn(1)
P(11)-Re(1)-Sn(1) 92.08(10)
P(12)-Re(1)-Sn(1) 86.32(10)
P(13)-Re(1)-Sn(1) 84.51(10)
C(4)-Sn(1)-C(3)
C(4)-Sn(1)-C(5)
C(3)-Sn(1)-C(5)
C(4)-Sn(1)-Re(1)
C(3)-Sn(1)-Re(1)
C(5)-Sn(1)-Re(1)
O(1)-C(1)-Re(1)
O(2)-C(2)-Re(1)
88.6(4)
94.6(4)
C(7)-Re(2)-P(23)
C(6)-Re(2)-P(23)
P(21)-Re(2)-P(23) 90.81(14)
88.2(5)
94.7(4)
the proposed attribution. Finally, the proton-coupled 119Sn NMR
spectra show a very complicated multiplet, owing to coupling
with the nine methyl protons and the phosphorus nuclei.
However, the proton-decoupled spectra are more simplified and
appear either as a triplet (7, 8) or an AB2M (M ) 119Sn)
multiplet (9), in agreement with the proposed formulation.
The perspective view of one of the two molecules found in
the asymmetric unit of the complex Re(SnMe3)(CO)2[P(OEt)3]3
(9b) is shown in Figure 3. Selected bond distances and angles
are given in Table 4. The two molecules are essentially identical,
within experimental error (see geometrical parameters in Table
4). The compound is similar to 6b, with the rhenium atom
coordinated by three phosphorus atoms of the phosphite ligands
in mer positions, two carbonyl ligands in cis positions, and a
tin atom with analogous geometrical parameters. However, some
differences can be found, apart from the change of a trihydri-
dostannyl for a trimethylstannyl ligand. First, the Re-C bond
distances are slightly different from those found in 6b, ranging
from 1.77(3) to 1.92(2) Å, and the shorter ones (1.77(3) and
1.81(2) Å) correspond to those trans to the phosphorus atom,
about 0.1 Å shorter than those trans to the trimethyltin ligand.
The Re-P bond distances range from 2.293(4) to 2.354(4) Å,
those mutually trans being slightly longer than that trans to the
carbonyl ligand, opposite to the case found for 6b.
85.7(4)
178.1(4)
C(7)-Re(2)-Sn(2)
C(6)-Re(2)-Sn(2)
(21)-Re(2)-Sn(2)
P(22)-Re(2)-Sn(2) 84.96(10)
P(23)-Re(2)-Sn(2) 84.86(9)
85.4(5)
177.4(4)
92.48(9)
99.1(6)
99.8(5)
C(10)-Sn(2)-C(8)
C(10)-Sn(2)-C(9)
C(8)-Sn(2)-C(9)
C(8)-Sn(2)-Re(2)
97.8(5)
101.0(6)
100.2(5)
119.9(4)
101.3(5)
119.2(3)
120.3(4)
113.6(3)
177.8(14)
179.1(13)
C(10)-Sn(2)-Re(2) 120.8(3)
C(9)-Sn(2)-Re(2)
O(6)-C(6)-Re(2)
O(7)-C(7)-Re(2)
113.5(4)
179.5(13)
175.5(17)
and by an X-ray crystal structure determination of the derivative
Re(SnMe3)(CO)2[P(OEt)3]3 (9b).
Diagnostic for the presence of the stannyl SnMe3 and Sn-
(CtCR)3 ligands are the 1H, 13C, and 119Sn NMR spectra. The
1H NMR spectra of the trimethylstannyl complexes M(SnMe3)-
(CO)nP5-n (7-9), beside the signals of the phosphites, show a
singlet at -0.10 to +0.22 ppm, with the characteristic satellites
119
119Sn
1
due to coupling with Sn (J H
between 32 and 42 Hz),
attributed to the methyl proton resonances of the SnMe3 ligand.
In the 13C NMR spectra, the carbon signal of the SnMe3 group
falls between -3.13 and -5.7 ppm, showing the characteristic
satellites due to the coupling with 119Sn, with J
Sn between
13C119
209 and 145 Hz. In an HMQC experiment, this signal was also
correlated with the proton singlet at -0.10 to +0.22 ppm, fitting
The Sn-C bond lengths are in the range of 2.18(1)-2.22(1)
Å, as found previously in the rhenium complex (dimethylchlo-

Stannyl Complexes of Mn and Re
Organometallics, Vol. 26, No. 11, 2007 2927
a
rotin)bis(η5-cyclopentadienyl)rhenium,24 other (triaryltin)rhe-
nium(I) complexes,21 and other (trimethyltin)metal complexes.25
As occurs in 6b, the substituents on the phosphorus atoms
mutually in trans positiond are situated in a pseudo-eclipsed
fashion, with torsion angles O-P-P-O of only 6.1(7)°
(average). However, another difference with respect to the
related complex is that one of the substituents follows the same
direction as the carbonyl ligand in the equatorial plane, with
O-P-Re-C torsion angles of 4.6(7)° (average), probably due
to the steric hindrance of the methyl groups on the tin ligand
(see Figure 3, bottom).
Scheme 5
The IR spectra of the tris(alkynyl)stannyl complexes
M[Sn(CtCR)3](CO)nP5-n (12-14: R ) p-tolyl) show a
medium-intensity band at 2131-2132 cm-1, attributed to the
νCtC band of the alkynyl group. In the spectra of the ethynyl
complexes [M]-Sn(CtCH)3 (10a, 11a), this band was not
observed, but an absorption at 3275-3269 cm-1, attributed to
the νCH band of the CtCH group, was observed. However, the
presence of the tris(alkynyl)stannyl ligand was confirmed by
the 13C and 119Sn NMR spectra. In addition to the signals of
CO and phosphite ligands, the 13C spectra of the derivatives
M[Sn(CtCR)3](CO)nP5-n (10a-14a) (Figures S3a and S3b,
Supporting Information) show two singlets, at 101-94 and
107-93 ppm, with the characteristic satellites due to coupling
with 119Sn and 117Sn nuclei, which were attributed to the CR
and Câ carbon resonances, respectively, of the Sn(CRtCâR)3
a Legend: [M] ) Re(CO)2P3 (15); P ) PPh(OEt)2 (a), P(OEt)3 (b).
SnH or (CH3)3SnCl species on appropriate complex precursors.
Nucleophilic substitution of chloride in the SnCl3 ligand thus
represents an interesting protocol2k for the synthesis of tin-
organostannyl complexes, which has allowed us to prepare metal
complexes containing tris(alkynyl)stannyl as a ligand for the
first time.1 In fact, numerous stannyl ligands SnR3 are known,
with many organic substituents, but none containing three
alkynyl groups have yet been reported.
Reactivity of Trihydridostannyl Complexes. The reactivity
of the coordinated tin trihydride group toward some substrates
was studied, and results are shown in Scheme 5.
13C119
The tin trihydride complexes [M]-SnH3 (4-6) quickly react
with carbon tetrachloride to give the trichlorostannyl derivatives
[M]-SnCl3 (1-3). The reaction is fast and cannot be controlled
to obtain the intermediate complexes [M]-SnH2Cl and [M]-Sn-
HCl24 in pure form. Even with CCl4 in a 0.4:1 ratio, a mixture
of chloro-hydrido stannyl derivatives was obtained, which
could not be separated. In every case, reaction with CCl4 to
give chloro derivatives is classical for transition-metal hydrides26
and seems to indicate the polyhydridic character of the SnH3
group.
Support for this hypothesis came from the reaction with
carbon dioxide, which quickly reacted with the dicarbonyl
complexes Re(SnH3)(CO)2P3 under mild conditions (1 atm, 25
°C) to give the tin bridging-hydroxo bis(formate) derivatives
[{Re{Sn[OC(H)dO]2(µ-OH)}(CO)2P3}]2 (15) as final products
(Scheme 5). However, a different behavior was shown by the
tricarbonyl complexes M(SnH3)(CO)3P2 (4, 5), whose reaction
with CO2 (1 atm) was very slow in the case of manganese. With
rhenium it gave an unstable formate compound, which decom-
posed during crystallization.
group. The J
Sn values between 312 and 187 Hz in one case
and between 69 and 37 Hz in the other clearly allow attribution
of the CR and Câ signals. Furthermore, in the spectra of ethynyl
Sn(CtCH)3 complexes (10, 11), the 13C signals at 94.1 ppm
(10a) and 97.2 ppm (11a) were also correlated, in an HMQC
experiment (Figure S4b, Supporting Information), with the
1
singlets at 2.53 (10a) and 2.20 (11a) ppm observed in the H
NMR spectra (Figure S4a, Supporting Information) and at-
tributed to ethynyl protons, in agreement with the presence of
the CtCH group. Finally, the 119Sn NMR spectra appear as a
triplet for the tricarbonyl complex 10, 12, and 13 and an AB2M
(M ) 119Sn) multiplet for dicarbonyl complexes 11 and 14
complexes, fitting the presence of the stannyl ligands.
The IR and NMR data of the derivatives M[Sn(CH3)3]-
(CO)nP5-n and M[Sn(CtCR)3](CO)nP5-n (7-14) also allow a
geometry in solution to be established. Thus, a mer-trans
structure (V, VII; Schemes 3 and 4) for tricarbonyls 7, 8, 10,
12, and 13 is supported by the three νCO bandssone of medium
intensity and two strongsobserved in the infrared spectra and
by the singlet that appears in the 31P spectra, indicating the
magnetic equivalence of the two phosphite ligands. Instead, a
mer-cis geometry (VI, VIII), like those observed in the solid
state for 9b, is proposed for the dicarbonyl compounds 9, 11,
and 14. In fact, the IR spectra show two νCO bands of two
carbonyls in mutually cis positions, while the 31P spectra show
AB2 multiplets, suggesting that the two phosphites are magneti-
cally equivalent and different from the third. In addition, the
13C spectra indicate that the two carbonyls are magnetically
nonequivalent, showing two multiplets for the carbonyl carbon
resonances, in agreement with the proposed geometry.
For information on the reaction path and the nature of the
intermediates, the progress of the reaction of Re(SnH3)(CO)2-
[P(OEt)3]3 (6b) with CO2 (1 atm) was monitored by NMR
spectra in the temperature range between +20 and -70 °C. As
the reaction proceeded, the 1H NMR spectra in CD3C6D5 at 20
°C showed the disappearance of the multiplet near 2.8 ppm of
the SnH3 group of the precursor and the appearance of
(26) (a) Muetterties, E. L. Transition Metal Hydrides; Marcel Dekker:
New York, 1971. (b) Dedieu, A. Transition Metal Hydrides; Wiley-VCH:
New York, 1992.
Complexes containing the trimethylstannyl ligand (SnMe3)
are known for several transition metals,1-3 including some
examples for manganese2e,6b,e,i,l and only one for rhenium,6e and
have often been obtained from the oxidative reaction of (CH3)3-
(27) The NMR data of the intermediate complex Re[SnH{OC(H)dO}2]-
(CO)2[P(OEt)3]3 ([A]) are as follows. 1H NMR (CD3C6D5, 25 °C; δ): 11.75
(s, br, 1 H, SnH), 8.70 (s, 2 H, CHO), 4.00 (m, 18 H, CH2), 1.23, 1.20 (t,
27 H, CH3). 1H NMR (CD3C6D5, -70 °C; δ): AB2X spin system, δX 11.92,
1
119
1 117
JAX ) JBX ) 0.1, J H Sn ) 1779 Hz (J H Sn ) 1703) (1 H, SnH), 8.84 (s,
2 H, CHO), 3.95 (m, 18 H, CH2), 1.21, 1.18 (t, 27 H, CH3). 119Sn NMR
(CD3C6D5, 25 °C; δ): AB2MX, δM -42.0, JAM ) 305.6, JBM ) 272.8, JAX
) JBX ) 0.1, JMX ) 1779. 31P{1H} NMR (CD3C6D5, 25 °C; δ): 116.7 (s,
br). 31P{1H} NMR (CD3C6D5, -70 °C; δ): AB2, δA 118.2, δB 117.9, JAB
(24) Belsky, V. K.; Protsky, A. N.; Molodnitskaya, I. V.; Bulychev, B.
M.; Soloveichik, G. L. J. Organomet. Chem. 1985, 293, 69-74.
(25) Clark, A. M.; Rickard, C. E. F.; Roper, W. R.; Woodman, T. J.;
Wright, L. J. Organometallics 2000, 19, 1766-1774.
117
117
) 47.7 (JA
) 288.9, JB
) 258.7).
Sn
Sn

2928 Organometallics, Vol. 26, No. 11, 2007
Albertin et al.
a
Scheme 6
Figure 4. ORTEP view of the complex [Re{Sn[OC(H)dO]2(µ-
OH)}(CO)2{P(OEt)3}3]2 (15b) drawn with thermal ellipsoids at the
20% probability level. The substituents on the phosphorus atoms
were removed for clarity.
was attributed30 to free H2 forming by hydrolysis of the Re-H
group. On the basis of these results, we propose the reaction
path shown in Scheme 6 for the formation of the µ-OH binuclear
complexes 15, which involves the initial insertion of two CO2
molecules into two Sn-H bonds of SnH3 to give the hydrido
bis(formate) intermediate [M]-SnH{OC(H)dO}2 of type [A],
which undergoes hydrolysis with H2O to give the final bridging-
hydroxo complexes 15. This reaction path also explains why
we were not able to isolate intermediate [A] in pure form, owing
to its fast reaction even with the traces of H2O present in
common “anhydrous” solvents, to give the final µ-OH deriva-
tives.
Insertion of CO2 into the M-H bond of classical hydrides is
well-known31,32 and has been studied as an important step of
its functionalization reaction. Insertion into the coordinated
Sn-H bond has no precedents,33 and our results may open the
way to the use of unconventional hydride species to activate
and functionalize the CO2 molecule. It is worth noting that Re-
(SnH3)(CO)2P3 (6) also reacts with CO2 in the solid state, giving
the final formate species 15. Exposure of solid samples of 6 to
CO2 (1 atm) gives first the intermediate Re[SnH{OC(H)dO}2]-
(CO)2P3 ([A]), which then undergoes hydrolysis with the traces
of H2O to give the final dinuclear species 15. Diffusion of CO2
through the crystals of the trihydridostannyl complexes 6
therefore yields formate species.
a Legend: [M] ) Re(CO)2P3 (15); P ) PPh(OEt)2 (a), P(OEt)3 (b).
resonances attributable to the hydridobis(formate)stannyl inter-
mediate Re[SnH{OC(H)dO}2](CO)2[P(OEt)3]3 ([A])27 (Scheme
6).
A singlet at 8.70 ppm, attributed to dCH of a formate group,
and a slightly broad signal at 11.75 ppm, with the characteristic
satellites of coupling with Sn isotopes, attributed to SnH proton
1
resonances, appeared in the H NMR spectra of the reaction
mixture. The proton-coupled 119Sn NMR spectrum also showed,
at -70 °C, a doublet of multiplets, due to coupling with one
hydride and the three phosphorus nuclei of the phosphites.
Taking into account that the 31P spectrum is an AB2 multiplet
at -70 °C, the 119Sn spectrum was simulated with an AB2MX
1
model (M ) 119Sn, X ) H), in agreement with the proposed
formulation for intermediate [A], which was the first product
of the reaction of 6b with CO2. We also attempted to isolate
this intermediate as a solid but always obtained the final dimeric
species 15. However, the formulation of intermediate [A] as
the hydrido bis(formate) complex [M]-SnH{OC(H)dO}2 was
confirmed by comparison of the spectroscopic data with those
of the related complex Os[SnH{OC(H)dO}2](Tp)L(PPh3) (L
) phosphite), previously obtained by us4 in a similar reaction
of the trihydridostannyl [Os]-SnH3 complex with CO2.
Compounds [Re{Sn[OC(H)dO]2(µ-OH)}(CO)2P3]2 (15) were
obtained as white microcrystals, stable in air and in solutions
of common organic solvents, where they behave as nonelec-
trolytes.16 Their formulation is supported by analytical and
1
spectroscopic data (IR and H, 13C, 31P, and 119Sn NMR) and
by the X-ray crystal structure determination of [Re{Sn[OC(H)d
O]2(µ-OH)}(CO)2{P(OEt)3}3]2 (15b), whose ORTEP diagram
is shown in Figure 4. Selected bond distances and angles are
given in Table 5. This compound was a dimeric complex in
which two octahedrally coordinated rhenium units are joined
by a bridging tetraformatebis(µ-hydroxo)ditin moiety. To our
knowledge, this is the first example found in the Cambridge
Crystallographic Database (CCDC,34 version 5.27, update Aug
The formation of binuclear µ-OH complexes such as 15 as
final products is not surprising and is the result of the oxophilic
nature of tin compounds,28,29 which can react with water to give
O and OH bridges in ring and cage compounds. We therefore
added an equimolar amount of H2O to the reaction mixture
containing the complex Re[SnH{OC(H)dO}2](CO)2[P(OEt)3]3
([A]) by microsyringe and observed the direct formation of the
binuclear bridging-OH complex [Re{Sn[OC(H)dO]2}(µ-OH)-
(CO)2{P(OEt)3}3]2 (15b) and of free H2. The 1H NMR spectra
did show the dC(H) formyl signal of the dimer at 8.85 ppm
and a singlet near 4.6 ppm, which decreased upon shaking and
(30) Crabtree, R. H.; Lavin, M.; Bonneviot, L. J. Am. Chem. Soc. 1986,
108, 4032-4037.
(31) (a) Pandey, K. K. Coord. Chem. ReV. 1995, 140, 37-114. (b) Jessop,
P. G.; Hsiao, Y.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1996, 119,
344-355. (c) Leitner, W. Coord. Chem. ReV. 1996, 153, 257-284. (d)
Yin, X.; Moss, J. R. Coord. Chem. ReV. 1999, 181, 27-59. (e) Jessop, P.
G.; Joo, F.; Tai, C.-C. Coord. Chem. ReV. 2004, 248, 2425-2442.
(32) (a) Whittlesey, M. K.; Perutz, R. N.; Moore, M. H. Organometallics
1996, 25, 5166-5169. (b) Field, L. D.; Lawrenz, E. T.; Shaw, W. J.; Turner,
P. Inorg. Chem. 2000, 39, 5632-5638 and references therein.
(33) Some studies on the reaction between Bu3SnH and CO2, giving
tributhylformate Bu3SnO2CH, were reported: Klingler, R. J.; Bloom, I.;
Rathke, J. W. Organometallics 1985, 4, 1893-1894.
(28) (a) Rivie`re, P.; Rivie`re-Baudet, M.; Satge´, J. In ComprehensiVe
Organometallic Chemistry; Wilkinson, G., Stone, F. G. A., Abel, E. W.,
Eds.; Pergamon Press: Oxford, U.K., 1982; Chapter 10. (b) Davies, A. G.;
Smith, P. J. In ComprehensiVe Organometallic Chemistry; Wilkinson, G.,
Stone, F. G. A.;, Abel, E. W., Eds.; Pergamon Press: Oxford, U.K., 1982;
Chapter 11.
(29) (a) Roesky, H. W.; Singh, S.; Jancik, V.; Chandrasekhar, V. Acc.
Chem. Res. 2004, 37, 969-981. (b) Shea, K. J.; Loy, D. A. Acc. Chem.
Res. 2001, 34, 707.
(34) Allen, F. H. Acta Crystallogr. 2002, B58, 380-388.

Stannyl Complexes of Mn and Re
Organometallics, Vol. 26, No. 11, 2007 2929
Table 5. Selected Bond Lengths (Å) and Angles (deg) for
Chart 1
[Re{Sn[OC(H)dO]2}(µ-OH)(CO)2{P(OEt)3}3]2 (15b)a
Re-C(2)
Re-P(2)
1.908(8)
2.370(2)
2.4127(18)
1.135(8)
2.040(4)
2.164(4)
2.164(4)
Re-C(1)
Re-P(3)
Re-Sn
C(2)-O(2)
Sn-O(42)
Sn-O(43)
1.957(8)
2.381(2)
2.7489(5)
1.161(8)
2.070(5)
2.245(5)
Re-P(1)
C(1)-O(1)
Sn-O(41)
Sn-O(41)i
O(41)-Sni
C(2)-Re-C(1)
C(1)-Re-P(2)
C(1)-Re-P(3)
C(2)-Re-P(1)
P(2)-Re-P(1)
C(2)-Re-Sn
88.1(3)
92.1(2)
87.0(2)
88.4(2)
C(2)-Re-P(2)
C(2)-Re-P(3)
P(2)-Re-P(3)
C(1)-Re-P(1)
P(3)-Re-P(1)
C(1)-Re-Sn
89.2(2)
90.4(2)
The Re-C bond distances, 1.908(8) and 1.957(8) Å, show the
different trans effects of the phosphite and the diformato-µ-
hydroxostannio ligands, the shorter one being that trans to the
tin atom. The Re-P bond distances range from 2.370(2) to
2.4127(18) Å, those mutually trans being about 0.04 Å shorter
than that trans to the carbonyl ligand. The bond values are
comparable with those mentioned previously in the case of Re-
(SnH3)(CO)2[P(OEt)3]3 (6b), in which the rhenium atom is
surrounded by similar atoms, although the Re-C bond trans to
the tin atom is 0.014 Å shorter and the Re-C bond trans to the
phosphorus atom is 0.022 Å longer.
The angles around the metal are quite regular and close to
the accepted value, except those concerning the tin atom, which
is slightly deviated from its expected position, probably due to
steric effects of the formato groups, and gives the C(2)-Re-
Sn angle a value of 172.6(2)°.
The IR spectra of the µ-hydroxobis(formate) complexes show
two medium-intensity bands at 1674-1594 cm-1, attributed31,32
to the νOCO,asym band of the two η1-formate OC(H)dO groups.
Variable-temperature NMR spectra indicate that the complexes
are fluxional, but the low-exchange limit spectra were obtained
already at -70 °C. At this temperature, the proton spectra show
one singlet at 9.72-9.21 ppm, attributed to the dC(H) of the
formate group, and one singlet at 8.91-8.90 ppm, attributed to
the hydroxo µ-OH proton resonance.
179.03(7)
174.4(2)
88.77(7)
85.87(19)
93.47(5)
174.8(6)
99.30(18)
84.65(18)
84.0(2)
92.10(7)
172.6(2)
86.83(5)
97.96(4)
176.1(7)
69.66(19)
81.57(17)
146.82(17)
116.65(13)
95.08(13)
P(2)-Re-Sn
P(3)-Re-Sn
P(1)-Re-Sn
O(1)-C(1)-Re
O(41)-Sn-O(42)
O(42)-Sn-O(41)i
O(42)-Sn-O(43)
O(41)-Sn-Re
O(41)i-Sn-Re
Sn-O(41)-Sni
O(2)-C(2)-Re
O(41)-Sn-O(41)i
O(41)-Sn-O(43)
O(41)i-Sn-O(43)
O(42)-Sn-Re
O(43)-Sn-Re
143.44(13)
117.84(11)
110.34(19)
a Symmetry transformations used to generate equivalent atoms: (i) -x,
-y, -z.
2006) with this tetraformatebis(µ-hydroxo)ditin moiety. It is also
the third complex described with the bis(µ-hydroxo)ditin moiety
coordinating to another metal atom through the two tin atoms.
As previously described complexes have involved iron,35 this
is the first reported example involving rhenium. Also, the
formate ion is barely used to bond the tin atom.36
Each tin atom has a highly distorted square pyramidal
geometry when the Re-Sn bond is considered. However, the τ
parameter shows only 6% distortion toward trigonal-bipyramidal
geometry.37 One of the formate oxygen atoms occupies the axial
position, with a Sn-O bond length of 2.070(5) Å. The other
formate oxygen atom, with a Sn-O bond length of 2.245(5)
Å, is in the basal plane, together with the two bridging hydroxyl
groups and the rhenium atom. The basal plane is highly distorted
(rms deviation of 0.3731) because, on one hand, the substituents
on the rhenium atom provide important steric requirements,
giving angle values of Re-Sn-O(41) ) 143.44(13)° (expected
180°) and Re-Sn-O(41i) ) 117.84(11)° (expected 90°) and,
on the other hand, the small O-Sn-O angle of the Sn2O2
distannoxane ring, 69.66(19)°. The Sn2O2 distannoxane ring is
planar but not regular, since the bridging hydroxyl groups
are asymmetric, with two Sn-O distances, 2.040(4) and 2.164-
(4) Å, analogous to the behavior seen in other Sn2O2 distan-
noxane rings.35a,38 The short Sn-Sn distance (3.4514(9) Å) is
longer than the Sn-Sn single bond (2.95 Å) found in tin
clusters.38
In addition to the signals of the phosphites, the 13C{1H} NMR
spectra show one singlet near 166 ppm, which was correlated
in an HMQC experiment (Figure S5b, Supporting Information)
with the formate proton signal at 9.72-9.21 ppm and attributed
to the carbon resonance of the formate dC(H) group. Instead,
no correlation with any 13C signal was observed for the proton
singlet of the hydroxo group at 8.91-8.90 ppm. We also
recorded the proton-coupled 13C spectra of 15b, which show a
doublet centered near 166 ppm with a JCH value of 200 Hz,
characteristic of a CH formyl resonance.32b The 119Sn spectra
of 15 appear as an A2BM (M ) 119Sn) multiplet, owing to
coupling with the phosphorus nuclei of phosphites, fitting the
proposed formulation. The IR and 31P NMR data also allow us
to establish a geometry in solution for the complexes. Thus, a
mer-cis geometry (IX; Chart 1), like that found in the solid state,
may be proposed for the dicarbonyl complexes [Re{Sn[OC-
(H)dO]2(µ-OH)}(CO)2P3]2 (15), on the basis of the A2B
multiplet observed in the 31P NMR spectra, and of the presence
of two strong νCO bands in the IR spectra. These two carbonyl
ligands are magnetically inequivalent, as suggested by the
presence of two well-separated multiplets in the carbonyl carbon
region of the 13C NMR spectra, in agreement with type IX
geometry.
The environment around the rhenium metal is a distorted
octahedron formed of three phosphorus atoms of phosphite
ligands, two carbonyl ligands in cis positions, and a tin atom.
(35) (a) Restivo, R.; Bryan, R. F. J. Chem. Soc. A 1971, 3364-3368.
(b) Pasynskii, A. A.; Grechkin, A. N.; Denisov, F. S.; Torubayev, Yu. V.;
Aleksandrov, G. G.; Dobrokhotova, Zh. V.; Lyssenko, K. A. Russ. J. Inorg.
Chem. 2002, 47, 1311-1316.
(36) (a) Donaldson, J. D.; Knifton, J. F. J. Chem. Soc. 1964, 4801-
4803. (b) Harrison, P. G.; Thornton, E. W. J. Chem. Soc., Dalton Trans.
1978, 1274-1278. (c) Molloy, K. C.; Quill, K.; Nowell, I. W. J. Chem.
Soc., Dalton Trans. 1987, 101-106. (d) Mistry, F.; Rettig, S. J.; Trotter,
J.; Aubke, F. Acta Crystallogr. 1990, C46, 2091-2093.
(37) Addison, A. W.; Rao, T. N.; van Reedijk, J.; Van Rijn, J.; Verschoor,
G. C. J. Chem. Soc., Dalton Trans. 1984, 1349-1356.
Conclusions
In this paper, we report the synthesis of the first stable
complexes of manganese and rhenium containing tin trihydride
as a ligand. Among the main properties shown by the [M]-SnH3
species is easy insertion of CO2 (1 atm) into the Sn-H bond,
(38) See, for example: (a) Duchateau, R.; W. Dijkstra, T.; Severn, J.
R.; van Santen, R. A.; Korobkov, I. V. Dalton Trans. 2004, 2677-2682.
(b) Chandrasekhar, V.; Thilagar, P.; Bickley, J. F.; Steiner, A. J. Am. Chem.
Soc. 2005, 127, 11556-11557.

2930 Organometallics, Vol. 26, No. 11, 2007
Albertin et al.
affording the binuclear tin formate complexes [Re{Sn[OC(H)d
O]2(µ-OH)}(CO)nP5-n]2. Structural parameters for both tin
trihydride complexes and bridging-OH tin formate derivatives
are also reported. The hydridic nature shown by the SnH3 group
leads us to regard our [M]-SnH3 compounds not only as metal
complexes containing SnH3 as a ligand but also as tin polyhy-
dride complexes stabilized by the M(CO)nP5-n fragment.
Nucleophilic substitution of chloride in the [M]-SnCl3 com-
plexes allows a new route for the synthesis of organostannyl
with Grignard compounds MgBrMe and MgBr(CtCH) or
lithium acetylides as reagents.
Acknowledgment. Mrs. Daniela Baldan is gratefully ac-
knowledged for technical assistance.
Supporting Information Available: NMR spectroscopic data
for selected compounds (Figures S1-S5) and CIF files giving
crystallographic data. This material is available free of charge via
the Internet at http://pubs.acs.org.
derivatives M(SnMe3)(CO)nP5-n and M[Sn(CtCR)3](CO)nP5-n
,
OM070220M