Table 4.

The g-values of Ru^III and Os^III complexes relevant to the present work with results from LFT analysis.

Complex a	gx, gy, gzi	Δ/ζh	V /ζh	V / Δ	k
nBu4N[1]	−1.31, −1.44, −2.44	−0.492	−0.043	0.088	0.8204
Na[1]	−1.37, −1.45, −2.50	−0.498	−0.026	0.053	0.8541
trans-[OsCl4(CO)(py)]−b	−2.55, −2.55, −1.72	+0.228	0.0	0	1.220
trans-[OsBr4(CO)(py)]−b	−2.50, −2.50, −1.80	+0.236	0.0	0	1.211
trans-[OsBr4(CO)2]−b	−2.46, −2.46, −1.81	+0.221	0.0	0	1.192
trans-[RuCl4(Him)2]−c	−3.12, −2.44, −1.2	+0.536	+0.316	0.589	1.256
trans-[RuCl4(Me2SO)2]−d	−2.35, −2.35, −1.87	+0.166	0.0	0	1.148
trans-[Ru(NH3)4(Him)2]3+e	−3.04, −2.20, (−0.15);	+0.9635;	+0.6043;	0.627;	1.002;
	−3.04, −2.20, (+0.15);	+1.136;	+0.7123;	0.627;	0.9667;
	(−0.9), −2.20, −3.04;	−0.6392;	−0.4016;	0.628;	1.114;
	(+0.9), −2.20, −3.04	−1.847	−1.160	0.628	0.9270
cis-[Ru(NH3)4(Him)2]3+e	−2.88, −2.14, (−0.65);	+0.6905;	+0.4265;	0.618;	1.003;
	−2.88, −2.14, (+0.65);	+1.463;	+0.9017;	0.616;	0.8360;
	−2.88, −2.14, (−0.15);	+0.9253;	+0.5357;	0.579;	0.9255;
	−2.88, −2.14, (+0.15)	+1.094	+0.6328	0.579	0.8858
[Os(NH3)5(H2O)]3+f	−2.3, −2.3, −1.22;	+0.3855;	0.0;	0.0;	0.9795;
	−2.2, −2.2, −1.08	+0.4097	0.0	0.0	0.8954
[Ru(NH3)5(H2O)]3+g	−2.620, −2.620, −0.6;	+0.7119;	0.0;	0.0;	1.052;
	−2.620, −2.620, (0.0)	+0.9878	0.0	0.0	0.9678
trans-[Ru(NH3)4(4-pic)(H2O)]3+h	−1.20, −1.56, −2.81	−0.671	−0.112	0.167	0.9378

^aCounterions are not given except for the two Os^III complexes reported here, but are noted for others below when relevant.

^bTaken from Kremer;³⁴ py = pyridine. The g values presented are all for complexes with tetraethylammonium countercation; for trans-Cs[OsCl₄(CO)(py)]: g_⊥ = 2.46, g_║ = 1.45.

^cTaken from Ni Dhubhghaill et al.⁸²

^dTaken from de Paula et al.⁸⁰ The g values reported are for the solid material; in aqueous or methanol solution, multiple species are reported due to replacement of Me₂SO and/or chlorido ligands by solvent.

^eTaken from Clarke et al.⁷⁷ The values for |g_min| were not observed (hence they are given in parentheses), but were proposed by their LFT analysis. In these systems, the proper choice of sign of the g values is not apparent based on standard criteria, namely the magnitudes of k or Δ, so both choices are given. Results of additional calculations are given; for the trans complex, using a value for |g_min| that would likely be the largest possible, but difficult to observe experimentally: |g_min| = 0.9; for the cis complex using the a value for |g_min| that would likely be the smallest possible: |g_min| = 0.15 (a value of zero is possible, but does not provide enough information for the fitting process). We favor the first entry listed in each case, which is in agreement with the model originally favored by Clarke et al.

^fTaken from McGarvey et al.^33c Two species are always observed in frozen aqueous solutions of [Os(NH₃)₅(H₂O)](CF₃SO₃)₃.

^gTaken from McGarvey et al.^33c The experimentally reported range for |g_min| is 0.0 ≤ |g_min| ≤ 0.6; we thus present calculations for both 0.6 and 0.0 – the minimum magnitude.

^hTaken from Souza et al.;³² 4-pic = 4-picoline (4-methylpyridine). The specific g values reported are those for frozen aqueous/ethylene glycol solution; those for a powder and in other solvents were similar.

ⁱThe signs of the g values are not determined experimentally, but are determined here by the model of McGarvey,^33b which provides two choices of sign. Only the more physically plausible choice of signs is presented, except when both choices are acceptable.