(Sn) Tin NMR

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ü Tin NMR	ü ^115Sn	ü Properties of ^115Sn
ü References	ü ^117Sn	ü Properties of ^117Sn
	ü ^119Sn	ü Properties of ^119Sn

Safety note: Some of the materials mentioned here are very dangerous. Ask a qualified chemist for advice before handling them. Qualified chemists should check the relevant safety literature before handling or giving advice about unfamiliar substances. NMR solvents are toxic and most are flammable. Specifically, tin may be toxic in large doses. Tin (IV) chloride reacts violently with water yielding corrosive and poisonous HCl.

Tin NMR

Tin is unique in that it has no less than three NMR active spin ½ nuclei, ¹¹⁵Sn, ¹¹⁷Sn and ¹¹⁹Sn, that yield narrow signals over a very wide chemical shift range. ¹¹⁹Sn is very slightly the more sensitive than ¹¹⁷Sn so ¹¹⁹Sn is therefore usually the preferred nucleus. ¹¹⁵Sn is much less sensitive than either ¹¹⁷Sn or ¹¹⁹Sn. Tin NMR is mostly used for the study of organotin compounds, but is also applicable to inorganic tin compounds.

Each type of tin compound has its characteristic chemical shift range.

Chemical shift ranges for tin NMR

Comparison of the NMR spectra of the tin isotopes ¹¹⁵Sn, ¹¹⁷Sn and ¹¹⁹Sn for SnCl₄ (neat)

All the tin nuclei couple to other nuclei, ¹H, ¹³C, ³¹P, ¹⁹F, etc., couplings have been reported. One bond couplings to ¹³C are getween 1500 and 1200 Hz. To ¹H one bond couplings are from 1750 to 3000 Hz, to ¹⁹F from 130 to 2000 Hz and to ³¹P they are from 50 to 2400 Hz. Two-bond Sn-H coupling constants are apporximately 50 Hz. Homonuclear ¹¹⁹Sn-¹¹⁹Sn and heteronuclear ¹¹⁹Sn-¹¹⁷Sn have been reported from 200 to 4500 Hz. Three and four bond couplings have been reported.

¹¹⁵Tin NMR

¹¹⁵Sn is much less sensitive than the other tin nuclei, so is not usually the preferred nucleus of tin. It is a spin ½ nucleus and yields sharp signals.

¹¹⁵Sn-NMR spectrum of SnCl₄ (neat)

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Properties of ¹¹⁵Tin

(Click here for explanation)

Spin	1/2
Natural abundance	0.34%
Chemical shift range	2600 ppm, from -1900 to 700
Frequency ratio (Ξ)	32.718749%
Reference compound	Me4Sn 90% in C6D6
Linewidth of reference	2.7 Hz
T1 of reference	0.65 s
Receptivity rel. to ^1H at natural abundance	1.24 × 10^-4
Receptivity rel. to ^1H when enriched	0.0365
Receptivity rel. to ^13C at natural abundance	0.711
Receptivity rel. to ^13C when enriched	209

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¹¹⁷Tin NMR

¹¹⁷Sn is slightly less sensitive than ¹¹⁹Sn so is not usually the preferred nucleus of tin. It is a spin ½ nucleus and yields sharp signals.

¹¹⁷Sn-NMR spectrum of SnCl₄ (neat)

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Properties of ¹¹⁷Tin

(Click here for explanation)

Spin	1/2
Natural abundance	7.68%
Chemical shift range	2600 ppm, from -1900 to 700
Frequency ratio (Ξ)	35.632259%
Reference compound	Me4Sn 90% in C6D6
Linewidth of reference	2.5 Hz
T1 of reference	0.65 s
Receptivity rel. to ^1H at natural abundance	3.54 × 10^-3
Receptivity rel. to ^1H when enriched	0.0461
Receptivity rel. to ^13C at natural abundance	20.8
Receptivity rel. to ^13C when enriched	271

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¹¹⁹Tin NMR

¹¹⁹Sn is slightly more sensitive than ¹¹⁷Sn and much more sensitive than ¹¹⁵Sn so is usually the preferred nucleus of tin. It is a spin ½ nucleus and yields sharp signals.

¹¹⁹Sn-NMR spectrum of SnCl₄ (neat)

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Properties of ¹¹⁹Tin

(Click here for explanation)

Spin	1/2
Natural abundance	8.59%
Chemical shift range	2600 ppm, from -1900 to 700
Frequency ratio (Ξ)	37.290632%
Reference compound	Me4Sn 90% in C6D6
Linewidth of reference	2.5 Hz
T1 of reference	0.65 s
Receptivity rel. to ^1H at natural abundance	4.53 × 10^-3
Receptivity rel. to ^1H when enriched	0.0527
Receptivity rel. to ^13C at natural abundance	26.6
Receptivity rel. to ^13C when enriched	310

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References

D. E. Williams, L. H. Toporcer and G. M. Ronk, "Nuclear magnetic resonance coupling constants in tin in 3,3,3-trifluoropropyltin compounds", J. Phys. Chem., 74, 2139-42 (1970).

E. V. Van den Berghe and G. P. Van der Kelen, "Study of the chemical bond in (CH₃)_nSn(SCH₃)_4-n(n=0,1,2,3) by NMR proton, tin-119, and carbon-13 spectroscopy", J. Organometal. Chem., 26, 207-13 (1971).

J. D. Kennedy, W. McFarlane and G. S. Pyne, "Effect of interbond angles at tin upon tin-119 chemical shifts in organotin alkane-α ,ω-dithiolates and some related compounds", Bull. Soc. Chim. Belg., 84, 289-298 (1975).

J. D. Kennedy, W. McFarlane, G. S. Pyne, P. L. Clarke and J. L. Wardell, "Magnetic double resonance studies of tin-119 chemical shifts in compounds with tin -sulfur bonds and related species", J. Chem. Soc., Perkin Trans. 2, 1234-1239 (1975).

T. N. Mitchell, "Substituent chemical shifts of the organotin moiety in compounds of the type RSnMe_nCl_3-n(n = 0 to 3; R = n-alkyl)", Org. Magn. Reson., 8, 34-39 (1976).

A. Tupciauskas, "Tin-119 NMR constants for organotin compounds with remote substituents", Lietuvos Fizikos Rinkinys, , 17, 233-238 (1977).

B. Wrackmeyer, "Carbon-13 and tin-119 NMR studies on alkynylstannanes", J. Organometal. Chem., 145, 183-188 (1978).

T. N. Mitchell, and G. Walter, " Fourier transform nuclear magnetic resonance investigations of organotin compounds. Part 6. Tin-119 and carbon-13 nuclear magnetic resonance. Spectra of hexaorganoditins and octaorganotritins", J. Chem. Soc., Perkin Trans. 2, (1977) 1842-1827.

R. Hani, and R. A. Geanangel, "Tin-119 NMR in coordination chemistry", Coordination Chem. Rev., 44, 229-246 (1982).

D. Dakternieks, R. W. Gable, and G. Winter, "Tin-119 and carbon-13 NMR studies on tin(IV) xanthates", Inorg. Chim. Acta, 75, 185-188 (1983).

K. Kobayashi, M. Kawanisi, T. Hitomi and S. Kozima, "Bonding isomers of triorganostannyl enolates analyzed by tin-119 NMR spectroscopy", Chem. Lett., 497-500 (1984).

H. Killing, H. and T. N. Mitchell, "New tin heterocycles: adducts between acetylenes or allenes and 'distannacyclopropanes'" Organometallics, 3, 1917-1919 (1984).

A. Lycka, M. Nadvornik, K. Handlir, and J. Holecek, "Carbon-13 and tin-119 NMR spectra of some triphenyltin 4-substituted benzoates dissolved in coordinating and non-coordinating solvents", Coll. Czech. Chem. Comm., 49, 2903-2911 (1984).

T. Yano, K. Nakashima, J. Otera, and R. Okawara, "Tin -119 NMR spectroscopic study on tetraorganodistannoxanes", Organometallics, 4, 1501-1503 (1985).

J. Bluemel, and F. H. Koehler, "Direct and indirect metallation of endo-dicyclopentadiene. Tin -119 and carbon-13 NMR studies of stannylated derivatives", J. Organometal. Chem., 340, 303-315 (1988).

T. N. Mitchell, J. C. Podesta, A. Ayala, and A. B. Chopa, "Experimental test of Karplus-type relationships for ³J(tin, carbon) and ³J(tin, hydrogen)", Magn. Reson. Chem., 26, 497-500 (1988).

I. Wharf, "Studies in aryltin chemistry. Part 5. Tin-119 and carbon-13 NMR spectra of some tetra- and triaryltin compounds", Inorg. Chim. Acta, 159, 41-48 (1989).

F. Thunecke, and R. Borsdorf, "Tin-119 NMR spectroscopic investigations of tributyltin derivatives of aromatic sulfonic acids", J. Prakt. Chem., 333, 489-494 (1991).

J. McManus, D. Cunningham, and M. J. Hynes, "Nuclear magnetic resonance and structural investigations of the chemistry of organotin compounds. II. ¹¹⁹Sn NMR investigations of the pyrazine adducts of dialkyltin(IV) dihalides", J. Organometal. Chem., 468, 87-92 (1994).

B. Wrackmeyer, M. Vosteen, and W. Storch, "Precise measurements of ^115/117/119Sn NMR frequencies and first observation of isotope-induced chemical shifts ¹Δ ^117/119Sn(¹⁵N), ¹Δ ^115/119Sn(¹⁵N), and ²Δ ^117/119Sn(²⁹Si) in N-trimethylstannyl amines", J. Mol. Struct., 602-603, 177-184 (2002).

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Updated 2007-02-26 © Roy Hoffman, Hebrew University 2007