result = subsref( cell2mat(vertcat(x{:})), struct('type', '()', 'subs', {{':', 2}}) );
This is why we seldom do it on a single line. Much easier is two lines, either of
col2 = @(M) M(:,2);
result = col2( cell2mat(vertcat(x{:})) );
or
temp2 = cell2mat(vertcat(x{:}));
result = temp2(:,2);
The advantage of the first approach is that the "col2" only needs to be defined once, so you can do similar operations with a single line afterwards
getcol = @(M, col) M(:,col);
result1 = getcol( cell2mat(vertcat(x{:})), 2);
result2 = getcol( cell2mat(vertcat(y{:})), 5);