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Journal of the American Chemical Society
S2ꢀS1 1.9526(9) Å, S1ꢀK1 3.2013(8) Å, O1ꢀK1 2.770(2) Å, standing of the fundamental chemistry of this important, but
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2
Cl1ꢀK1 3.2674(8) Å, O1ꢀN1ꢀS2 119.6(1)°, N1ꢀS2ꢀS1
113.27(7)°.
poorly understood, ion.
ASSOCIATED CONTENT
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The isolation of 3 from the reaction of [K(18ꢀcrownꢀ
6)][(LtBu)NiII(S)] with NO demonstrates for the first time that a
transition metal sulfide can react with NO to form [SSNO]ꢀ, an
observation that may have implications for our understanding
of the reactions between NO and sulfurꢀcontaining metalloꢀ
proteins in vivo.5,6 To account for the formation of 3, we hyꢀ
pothesize that the first step of the transformation involves sulꢀ
fur abstraction by NO, forming "[K(18ꢀcrownꢀ6)][SNO]" and
“[(LtBu)NiI]”. Subsequent reaction of “[(LtBu)NiI]” with NO
yields complex 2 (Scheme 1a), a transformation that has been
observed previously.33 Separately, reaction of "[K(18ꢀcrownꢀ
6)][SNO]" with NO results in formation of complex 3
(Scheme 1b). Alternatively, it is possible that the first step of
the reaction yields a nickelꢀSNO adduct, e.g., [K(18ꢀcrownꢀ
6)][(LtBu)Ni(SNO)], which subsequently reacts with NO to
yield the final products. To test this hypothesis we monitored
the reaction of [K(18ꢀcrownꢀ6)][(LtBu)NiII(S)] with only 1
equiv of NO, which resulted in only partial consumption of
[K(18ꢀcrownꢀ6)][(LtBu)NiII(S)], and formation of complex 2 as
the only identifiable Niꢀcontaining product (Figures S6ꢀS7).
These two complexes are present in an approx. 1:2 ratio, reꢀ
spectively. The observation of unconsumed [K(18ꢀcrownꢀ
6)][(LtBu)NiII(S)] is consistent with the proposed mechanism,
assuming that the sulfide abstraction step is rate determining.
In addition, we monitored the reaction of independently preꢀ
pared [PNP][SNO]30 with nitric oxide by UVꢀvis spectroscopy
(eq 2). Thus, exposure of an MeCN solution of [PNP][SNO]
to excess NO resulted in complete consumption of
[PNP][SNO], as revealed by the loss of the absorption band at
334 nm, and the generation of [PNP][SSNO], as revealed by
the appearance of a new band at 445 nm (Figure S14). The
other products generated in the transformation remain unidenꢀ
tified; however, we can rule out formation of N2O as it could
not be detected in reaction mixture by either gas chromatogꢀ
raphy or IR spectroscopy. While conversion of [SSNO]ꢀ to
[SNO]ꢀ was previously reported,34 this is the first demonstraꢀ
tion that [SNO]ꢀ can be converted into [SSNO]ꢀ upon oxidaꢀ
tion.
Supporting Information. Experimental procedures, crystalloꢀ
graphic details (as CIF files), and spectral data for complexes 1-3.
This material is available free of charge via the Internet at
AUTHOR INFORMATION
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Corresponding Author
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
We thank the National Science Foundation (CHE 1361654) for
financial support of this work. This research made use of the 400
MHz NMR Spectrometer of the Chemistry Department, an NIH
SIG (1S10OD012077ꢀ01A1).
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In summary, the “masked” terminal nickel sulfide complex,
[K(18ꢀcrownꢀ6)][(LtBu)NiII(S)], readily activates CO to give a
carbonyl sulfide complex, [K(18ꢀcrownꢀ6)][(LtBu)NiII(S,C:η2ꢀ
SCO] (1), via CO addition across the NiꢀS bond. This result
further highlights the high nucleophilicity of the sulfide ligand
in [K(18ꢀcrownꢀ6)][(LtBu)NiII(S)], despite the K+ capping moiꢀ
ety that is present in both solution and the solidꢀstate. Moreoꢀ
ver, complex 1 represents a wellꢀdefined example of a late
metal [COS]2ꢀ adduct.9,30ꢀ32 The sulfide ligand in [K(18ꢀcrownꢀ
6)][(LtBu)NiII(S)] also activates NO to generate a nickel nitroꢀ
syl, [(LtBu)Ni(NO)] (2), and a perthionitrite salt, [K(18ꢀcrownꢀ
6)][SSNO] (3). This result represents the first confirmed genꢀ
eration of [SSNO]ꢀ from reaction of transition metal sulfide
with NO. This observation is significant because it further
confirms that metal sulfides can play a regulatory role in vivo
with respect to NO availability (e.g., soꢀcalled NO/H2S “cross
talk”).4,36,37 We have also discovered that oxidation of [SNO]ꢀ
with NO results in formation of [SSNO]ꢀ. This represents a
new route to [SSNO]ꢀ, and provides us with a better underꢀ
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(14) Pomowski, A.; Zumft, W. G.; Kroneck, P. M. H.; Einsle,
O. Nature 2011, 477, 234.
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