We first investigate the fac-Re(CO)3(CH3CN)3 + •N2 complex (Fig. ) in the carbonyl stretch region. There are two features in the linear IR spectrum, a doubly-degenerate asymmetric carbonyl stretch near 2000 cm -1 and a symmetric carbonyl stretch near 2080 cm -1 (top panel Fig. ). The bottom panel of Fig. presents the previously reported TA-CIVS spectra at 200 fs and 400 fs waiting times, showing relatively strong bleaching signals at the two fundamental frequencies. Importantly, there are notable intensity differences between the two spectra. Our previous measurements showed intensity modulations in both bleach signals with a period of ~417 fs, matching the energy difference between the two transitions. The presence of such oscillations with pump-probe waiting time are indicative of strong coherent coupling between the vibrational modes. 14, The implied presence of mode coupling are expected to manifest as off-diagonal cross peaks between the symmetric and asymmetric carbonyl stretches in a 2D IR spectrum. 2D-CIVS spectra at 208 fs (TA minimum) and 417 fs (TA maximum) waiting times are presented in Figs. and, respectively. Cross-peak features between the carbonyl stretch transitions are clearly recovered, as anticipated, in addition to the diagonal bleach signals. The cross peaks and overall signal are stronger at Tw = 417 fs compared to 208 fs, consistent with the TA spectra and reported solution-phase 2D IR spectra of metal-carbonyl complexes. Note that the 2D-CIVS spectra were collected in the ZZZZ polarization scheme (all pulses parallel). Since the asymmetric and symmetric carbonyl stretches have orthogonal transition moments, cross-peak signal will be strongest in the ZZYY scheme. The 2D lineshapes, in general, appear homogeneously broadened with little apparent inhomogeneous diagonal elongation. This is, perhaps, not too surprising given the dilute, solvent-free environment and cryogenic conditions.