If it is soluble in a suitable solvent (e.g. D2O) proton NMR might help with the glycosidic linkage question. If the transition metal affects nuclear relaxation rates, NMR might also help with the complexation question.
Hi, the most simple way is to use edited HSQC spectrum. If 1,6- linkage is present in your polysaccharide you should see H6,H6´/C6 cross peaks shifted to cca 70ppm for carbon. Otherwise, if you need detailed structural features of your polymer, this question can be answered (after a complete assignment of protons for each sugar unit) by NOESY, ROESY or HMBC experiment.